Alice  iiamilton 


Industrial  poisoning  in  making  coal-tar  dyes  and 
dye  intermediates. 


QMiAt.ar 


His. 


College  of  ^tp^idanss  mh  ^urgeong 
ILihxatv 


Digitized  by  tine  Internet  Arcinive 

in  2010  witii  funding  from 

Open  Knowledge  Commons 


http://www.archive.org/details/industrialpoisonOOhami 


U.  S.  DEPARTMENT  OF  LABOR 

JAMES  J.  DAVIS,  Secretary 

BUREAU  OF  LABOR  STATISTICS 

ETHELBERT  STEWAkT,  Commissioner 


BULLETIN  OF  THE  UNITED  STATES)  (  VT^     IQfi 

BUREAU  OF  LABOR   STATISTICS/  '  '   '  '   '    {  nU,    C*0\j 

INDUSTRIAL       ACCIDENTS       AND       HYGIENE       SERIES 


INDUSTRIAL  POISONING  IN 
MAKING  COAL-TAR  DYES 
AND  DYE  INTERMEDIATES 

By  ALICE  HAMILTON,  M.  A.,  M.  D. 


APRIL,  1921 


WASHINGTON 

GOVERNMENT  PRINTING  OFFICE 

1921 


'0*i'ij 


PUBLICATIONS  OF  THE  BUREAU  OF  LABOR  STATISTICS. 

The  publication  of  the  annual  and  apedal  reports  and  of  the  bimonthly  bulletin  has 
been  discontinued,  and  since  July.  1912,  a  bulletin  has  been  published  at  irregular  intervals. 
Each  number  contains  matter  devoted  to  one  of  a  series  of  general  subjects.  These  bulletins 
are  numbered  consecutively  in  each  series  and  also  carry  a  consecutive  ichole  number,  ' 
beginning  with  No.  101.  A  complete  list  of  the  reports  and  bulletins  of  the  bureau  will  be 
furnished  on  application. 

A  list  of  the  series  of  bulletins  now  published  by  the  bureau  is  as  follow: 

'Wboleiale  Priceg. 

Retafl  Prices  and  Cost  sf  Lirins:. 

Wages  and  Hours  of  Labor. 

EmpIoTment  and  UnempIoTinent. 

Women  in  Industry. 

Workmen's  Insurance  and  Compensation  (induding  laws  relating  tiiereta). 

Indostrial  Accidents  and  Hygiene. 

Conciliation  and  Arbitration   (including  strikes  and  lockouts). 

Labor  Laws  of  the  United  States  (including  decisions  of  courts  relating  to  Utor). 

Foreign  Labor  Laws. 

Vocational  Education. 

Labor  as  Affected  by  the  War. 

MisceDaneouB  Series. 

INDUSTRIAL  ACCIDENTS  AIJD  HYGIENE. 

Prior  to  the  publication  of  the  bulletins  of  the  Bureau  in  the  present  form,  many  reportm^ 
were  issued  devoted  wholly  or  in  part  to  the  subjec  of  "  Industrial  Accidents  and  Hygiene."  5 
For  a  full  list  of  these  the  reader  is  referred  to  Bulletin  174.  Subject  Index  of  the  Publica- 
tions of  the  Bureau  of  Labor  Statistics,  up  to  May  1, 1915.  Reports  dealing  with  the-subject] 
are  as  follows: 

•Bui.  40,  May,  1902,  Report  of  French  Bnrean  of  Labor  regarding  Indastrlal  hygiene. 
•Bnl.  44,  January,  1903,  Factory  sanitation  and  labor  protection. 
•Bui.  67,  NoTcmber,  1906,  Austrian  lead  and  zinc  works,  1904. 
♦Bui.  72,  September,  1907,  Health  of  Cornish  miners,  1902. 
•Bui.  75,  March,  1908,  Industrial  hygiene. 

•Bui.  77,  July,  1908,  Compensation  for  Industrial  diseases.  Great  Britain,  1906. 
•Bui.  79,  November,  1908,  Mortality  from  consumption  in  dusty  trades. 
•Bui.  80,  January,  1909,  Compensation  for  industrial  diseases.  Great  Britain,  1908, 
•Bui.  82,  May,  1909,  Mortality  from  consumption  in  occupations  exposing  to  munici- 
pal and  general  organic  dust. 
•Twenty-fourth    Annual    Report,    1909,    Workmen's    insurance    and     compensation 

systems  in  Europe. 
•Bnl.  86,  January,  1910,  Phosphorus  poisoning  In  the  match  Industry  in  the  United 
States. 

List  of  Industrial  poisons. 
•Bui.  89,  July,  1910,  Child-labor  legislation  in  Europe. 

•Bui.  92,  January,  1911,  Kesolutlons  of  the  sixth  delegates'  meeting  of  the   Inter-  ■ 

national  Association  for  Labor  Legislation :  Industrial  poisons. 

Report  of  Illinois  Commission  on  Occupational  Diseases, 

•Bui.  95,  July,  1911,  Industrial  lead  poisoning  in  Great  Britain  and  western  Europe^; 

The  white-lead  industry  In  the  United  States,  with  an  appendix  on  the  lead-^ 

oxide  Industry. 
Deaths  from  Industrial  lead  poisoning  in  New  York  State  In  1909  and  1910. 
Laws  enacted  during  1911  requiring  the  report  of  occupational  diseases. 
•Bnl.  96,  September,  1911,  Attitude  of  Massachusetts  employers  toward  the  health 
of  their  employees. 
1911,  Conditions  of  employment  In  the  Iron  and  steel  Industry  in  the  United  Stat 
(S.  Doc.  110,  62d  Cong.,  Ist  sess.).  Vol.  IIL 


•  Supply  exhausted. 

[See  also  third  page  of  eoven,-'' 


S.  DEPARTMENT  OF  LABOR 

JAMES  J.  DAVIS,  Secretary 

BUREAU  OF  LABOR  STATISTICS 

ETHELBERT  STEWART,  Commissioner 


BULLETIN  OF  THE  UNITED  STATES  \ 
BUREAU    OF    LABOR    STATISTICS/ 


2 


INDUSTRIAL        ACCIDENTS        AND        HYGIENE        SERIES 


By  ALICE  HAMILTON,  M.  A.,  M.  D. 


APRIL,  1921 


WASHINGTON 

GOVERNMENT  PRINTING  OFFICE 

1921 


Hi2 


CONTENTS. 


Page. 

Introduction 5-7 

Beuzeue,  toluene,  and  xylene 7-11 

Benzene  derivatives 11-36 

The    nitro    compounds 18-25 

Niti-obenzenes? 18-20 

Nitrotoluenes 20-22 

Nitronaphthalenes 22 

Kitranisols 22 

Dinitrophenol  1-2-4 - 22-25 

Anilin  and  other  amido  compounds ■ 25-34 

Toluidins 28-30 

Xyliding : 30 

Diamines :  Toluylendiamine,  pheuylendiamines,  quinone  dichlor- 

diamine 30,  31 

Diphenylamine '■ —        31 

Nitranilins 31,  32 

Metliyl  and  ethyl  anilin 32,33 

Anilin  hydrochloride.     Sulfauilie  acid S3 

Paraamidophenol 33 

Naphthylamines 33,  34 

Amidoazotoluene 34 

Chlor  compounds 34,  35 

Chlorbenzene 34 

Nitrochlorbenzene 35 

Dinitrochlorbenzene 35 

Benzyl  chloride,  benzal  chloride,  chlorinated  toluene 35 

Hydroxy  compounds 36 

Pyridins 36 

Phosgene  or  carbonyl  chloride 36.  87 

Alipliatic  or  fatty  compounds 37-41 

Methyl  alcohol  or  Vi'ood  alcohol 88 

Formaldehyde 38,  39 

Acetone 39 

Dimethyl  sulphate . 39-41 

Methyl  chloride 41 

Inorganic  compounds 42-4G 

Hydrochloric,  sulphuric,  and  nitric  acids 42,  43 

Hydrogen  sulphide  or  sulphuretted  hydrogen 43,  44 

Plydrogen  arsenide  or  arseniuretted  hydrogen 44—16 

Caustics 40 

Records  of  sickness  in  German  dye  manufacture 47 

Piecords  of  sickness  in  American  dj^e  works 48-50 

Processes  in  dye  manufacture 50-58 

1.  Suiphonation 51 

2.  Caustic  fusion 51,52 

-^         3.  Nitration 52,  53 

J        4.  Reduction 53-56 

5.  Chlorination 56 

6.  Alkylation 56,  57 

7.  Oxidation 57 

8.  Carboxylation 57 

9.  Liming 57 

10.  Condensation 57 

^       11.  Diazotizing  and  coupling 57,  58 

f  3 


4.  C017TENTS. 

Page. 

Color  manufiictiire PflrQ 

Prevention  ol^  occupational  poisoning 7— .— -"7""T  ^^'^ 

Appendix   1.— Structure   of   the  benzene   rmg   and  its   principal   den\a- 

tives,  isomeric  forms,  etc —- '^  '^ 

Appendix  2.— Diagram  of  the  products  derived  from  coal  and  some  ot 

■|-]ip1 1»    iiSGS ^ 

Appendix^  3.— Massachusetts :  Rules  and  regulations  suggested  for  safety 
in  the  manufacture  of  benzene  derivatives  and  explosives _— _-    i^i-ii 

Appendix  4.— New  Jersey  and  Pennsylvania :   Safety   standards  lor  the  ^ 
manufacture  of  nitro  and  amido  compounds -~T— '  ' '  '^''^ 

Appendix  5 —Great  Britain:  Eegulations  for  the  manufacture  of  mtro^ 
and  amido  derivatives  of  benzene  and  of  explosives  with  the  use  01 
dinitrobenzol  or  dinitrotoluol 


BULLETIN  OF  THE 
U.  S.  BUREAU  OF  LABOR  STATISTICS. 

NO.  280.  WASHINGTON.  April,  1921 


INTRODUCTION. 

The  making  of  coal-tar  dyes  and  dye  intermediates  in  the  United 
States  has  grown  enormously  since  1914,  and  during  this  time  the 
industry  has  passed  through  miany  phases.  The  author's  first  ac- 
quaintance with  it  was  in  1916-17,  when,  in  the  course  of  an  investi- 
gation of  plants  manufacturing  and  loading  explosives,  a  number 
that  were  also  manufacturing  dye  intermediates  were  visited.  More- 
over, some  compounds  are  used  for  both  purposes;  for  instance, 
dinitrotoluene,  dinitrobenzene,  diphenjdamine,  and  aniiin.  At  that 
time  the  methods  used  were  sometimes  crude  and  decidedly  dangerous, 
because  it  was  only  in  a  few  old  plants  that  the  nature  of  these  com- 
pounds was  well  understood,  the  risks  known,  and  the  proper  pre- 
cautions taken.  It  was  generally  believed  that  vapors  were  the 
greatest  danger;  that  men  became  poisoned  by  brea,thing  fumes  of 
volatile  liquids,  and  when  preventive  measures  were  undertaken  they 
were  based  on  this  idea.  It  was  only  later  that,  as  a  result  of  sad  ex- 
perience, certain  solids,  such  as  dinitrobenzene  and  paranitranilin, 
were  discovered  to  be  quite  as  troublesome  as  a  volatile  liquid  like 
aniiin,  or  even  more  so.  It  was  also  found  that  one  could  not  revive  a 
man  with  aniiin  poisoning  by  taking  him  out  in  the  fresh  air ;  one  must 
also  get  rid  of  the  aniiin  on  his  skin  by  stripping  and  bathing. 

Gradually  the  results  of  experience  became  known  and  conditions 
improved  more  or  less.  The  improvement  was  hastened  by  the  closing 
of  the  smaller  works  and  by  the  concentration  of  S.je  intermediate 
manufacture  in  a  few  large  plants.  While  in  1916  aniiin  and  nitro- 
benzene were  made  in  dozens  of  places,  they  are  now  made  in  only 
a  few,  and  there  has  been  a  very  decided  falling  off  in  the  cases  of 

«  This  report  is  based  on  36  inspections  of  American  plants  producing  crudes,  inter- 
mediates, and  colors,  made  during  the  years  1916  to  1919,  and  on  visits  to  the  following 
foreign  works  during  the  summer  of  1919:  British  Dyes  (Ltd.),  Huddersfield  ;  Levinstein 
(Ltd.),  Manchester;  Claus  &  Co.  (Ltd.),  Clayton,  Manchester;  Clayton  Aniline  Co.  (Ltd.), 
Clayton,  Manchester  ;  Mersey  Chemical  Co.,  near  Liverpool  ;  Poiret  &  Cie.,  St.  Denis,  near 
Paris  ;  Allgemeine  Chemische  Gesellschaft,  Basel ;  Leopold  Casella,  Mainkur,  near  Frank- 
fort-on-the-Main. 


6  I^iDUSTEIiyL   POISOXIXG   IX    MAKIXG   COAL-TAE   DYES. 

intoxication  from  these  compounds.  There  has  also  been  a  great  im- 
provement in  the  care  given  to  the  employees.  The  larger  plants 
have  safety  or  welfare  superintendents,  whose  dut}-  is  to  provide 
against  accidents  and  accidental  poisoning.  Physicians  are  em- 
ployed to  attend  such  cases,  and  these  physicians  acquire  skill  in 
diagnosis  and  treatment  which  can  not  be  obtained  by  the  ordinary 
practitioner.  In  the  best  American  plants  the  physicians  also  do 
very  valuable  preventive  work.  The  competent  physician  is  familiar 
with  the  different  processes  and  the  dangers  inherent  in  them,  and 
keeps  watch  for  the  earliest  symptoms  of  occupational  intoxication 
among  the  men.  The  manufacture  of  dyes  and  intermediates  in  the 
T^nited  States  has  undergone  great  improvement  and  is  improving 
from  day  to  day,  but  it  can  not  be  said  that  this  improvement  is  at 
ail  uniform  or  that  there  are  not  still  some  unnecessarily  dangerous 
departments  even  in  the  best  plants,  and  a  few  are  still  far  from 
what  they  should  be,  both  in  the  matter  of  construction  and  operation 
and  in  the  personal  care  of  the  force.  It  is  because  of  this  great 
variation,  this  lack  of  standardization  of  the  safety  work  in  the  in- 
dustry, that  it  seems  useful  to  present  the  results  of  an  investigation 
carried  on  at  intervals  during  the  last  three  j'^ears,  so  that  the  dif- 
ferent manufacturers  may  learn  of  the  methods  used  in  places  other 
than  their  own  and  the  experience  gathered  in  one  place  may  be 
made  available  for  all  places  doing  similar  work. 

It  seems  valuable  also  to  publish  in  convenient  form  the  informa- 
tion that  can  be  gathered  from  the  literature,  especially  of  Germany, 
concerning  the  action  on  the  human  body  of  the  great  varietj^  of 
compounds  used  in  this  complicated  industry.  Germany  has  for 
years  conducted  elaborate  animal  experiments  vfith  these  compounds, 
and  in  addition  an  enormous  human  experiment  has  gone  on  in  her 
dye  works.  It  seems  a  pity  not  to  avail  ourselves  of  the  results 
rather  than  to  go  on  and  repeat  such  human  experiments  ourselves. 
Of  late,  American  observers  have  added  their  contribution  to  this 
branch  of  industrial  toxicology,  and  wherever  possible  the  Ameri- 
can publications  have  been  used.  The  compounds  that  are  dealt 
with  in  this  report  are  not  by  any  means  all  that  the  color  worker 
comes  in  contact  with.  Others,  whose  chemical  composition  leads 
one  to  suspect  that  they  possess  toxic  jDroperties,  may  later  on  prove 
to  be  quite  as  dangerous  as  those  about  which  we  already  have 
sufficient  data  to  indicate  their  poisonous  character.  The  only  ones 
taken  up  in  this  report  are  those  which  have  been  found  to  cause 
actual  poisoning  in  human  beings. 

One  advantage  the  American  industry  possesses  when  compared 
with  the  European  is  the  absence  of  women  in  the  working  force. 
During  1918  plans  were  under  way  to  substitute  women  for  men  in  a 
few  plants,  and  some  women  were  actually  employed,  but  as  soon 
as  the  armistice  was  signed  the  women  were  discharged  and  there  is 
no  intention  now  of  employing  them  in  any  plant.  This  is  a  matter 
for  congratulation  because  it  is  believed  by  all  authorities  that  the 
employment  of  women  in  work  exposing  them  to  any  poison  should 
be  discouraged  as  much  as  possible,  not  because  they  are  necessarily 
more  susceptible  to  poison  than  men,  but  because  if  they  do  suffer 
from  the  effects  they  may  pass  the  injurj^  on  to  their  offspring. 

The  rei)ort  is  not  presented  as  a  complete  one  in  any  sense,  cer- 
tainly^ not  as  a  complete  description  of  the  processes  used  in  dye  and 


INTRODUCTIOIsr.  7 

dye  intermediate  manufacture.  Only  tbe  barest  outline  of  these 
processes  is  attempted,  and  this  merely  because  the  dangers  of  the 
work  can  not  be  described  without  some  such  slight  outline  of  the 
chief  reactions  and  their  resulting  compounds. 

The  making  of  dj^es  has  necessitated  the  production  and  use  not 
only  of  benzene,  nitrobenzene,  and  anilin,  but  also  of  an  enormous 
number  of  derivatives,  many  of  which  have  a  toxic  action  on  the 
skin,  on  the  central  nervous  system,  on  the  blood,  or  on  all  three. 
The  crude  compounds  of  the  coal-tar  series  that  serve  as  starting- 
points  for  the  production  of  dyes  are  benzene,  toluene,  xylene, 
naphthalene,  anthracene,  and  phenanthrene,  the  first  three  of  which 
are  decidedly  toxic.  Naphthalene  was  tested  by  Eulenberg^  who 
says  that  it  causes  in  animals  nothing  worse  than  an  irritation  of 
the  mouth,  nose,  and  eyes,  with  salivation  and  lachrymation.  Men  em- 
ployed with  hot  naphthalene  may  suffer  from  headache  and  confu- 
sion caused  by  the  fumes,  Eulenberg  found  the  same  effect  from 
hot  anthracene,  and  also  occasionally  an  eczema. 

BENZENE  (CgHe),  TOLUENE  (CeHgCHg),  AND  XYLENE 

(CeH,(CH,),), 

Benzene  is  obtained  in  this  country  in  the  manufacture  of  coke 
and  of  illuminating  gas.  In  coke  works  the  coal  is  roasted  and  the 
lighter  vapors,  benzene,  toluene,  and  xylene^  are  absorbed  in  heavier 
oils  with  a  higher  boiling  point,  and  are  then  subjected  to  fractional 
distillation.  Benzene  and  its  homologues  are  also  recovered  from 
coal-gas  residuals  in  gas  works.  In  making  gas  the  tar  left  in  the 
mains  and  scrubbers  is  allowed  to  stand  till  the  gas  liquor  separates 
out,  a  source  for  the  obtaining  of  ammonia,  then  the  tar  is  distilled. 
The  first  bodies  to  pass  over  are  benzene,  toluene,  and  X3dene;  next 
come  crude  carbolic  acid  and  naphthalene  "  dead  oil,"  then  anthra- 
cene, leaving  a  residue  of  coal-tar  pitch. 

In  well-constructed  and  well-managed  plants  for  the  production 
of  these  bodies  there  is  practically  no  danger  of  fumes  or  contact 
with  the  volatile  poisonous  substances  except  when  it  is  necessary  to 
repair  or  clean  the  apparatus.  When  this  is  done  extraordinary  pre- 
cautions must  be  taken  to  protect  the  men,  and  sometimes  in  spite 
of  these  precautions  very  serious  accidents  occur.  The  same  thing 
is  true  of  the  use  of  the  light  coal-tar  distillates  in  making  dye  in- 
termediates; the  cases  of  industrial  poisoning  follow  almost  always 
some  accident  or  an  unusual  exposure  in  the  course  of  a  job  of  clean- 
ing or  repairing. 

Benzene  is  a  fairly  new  industrial  poison  in  the  United  States,  for 
its  use  before  the  war  was  decidedly  restricted,  since  it  was  imported 
from  Germany  and  therefore  expensive.  The  petroleum  products, 
naphtha,  benzine,  and  gasoline,  were  used  as  solvents 'for  fats,  gums, 
and  rubber,  because  they  were  obtainable  in  large  quantities  in  this 
country.  After  the  outbreak  of  the  war  there  v/as  a  sudden  demand 
for  toluene  for  the  manufacture  of  trinitrotoluene  and  of  benzene  for 
the  manufacture  of  picric  acid  and  tetryl,  and  at  the  same  time  the 
coal-tar  dye  industrj'-,  which  was  growing  with  great  rapidity,  added 

^  Quoted  by  Koclscli  in  Miiiichcner  mcdizinische  Wochenschrift,  July  24,  1917. 


8  Il^DUSTEIAL   POISOFIiSTG   IX    MAKIXG    COAL-TAK   DYES. 

its  demand  for  these  two  compounds,  and  the  rubber  industry,  which 
had  become  dependent  upon  German  anilin,  was  obliged  to  procure 
benzene  and  manufacture  aniiin.  At  present  Large  quantities  of  tar 
distillates  are  produced  in  the  United  States  and  used,  not  only  in  the 
manufacture  of  dyes,  drugs,  and  perfumes,  but  also,  because  of  their 
powerful  solvent  properties,  in  rubber  manufacture  and.  in  the  mak- 
ing of  shellacs,  varnishes,  varnish  and  paint  removers,  and  dope  for 
airplanes.  They  are  also  coming  into  increasing  use  as  fuel  for  motor 
cars.  In  consequence  of  this  large  production  and  use  we  have  had 
during  the  last  five  years  a  much  larger  number  of  cases  of  industrial 
poisoning  from  benzene  and  toluene  than  were  reported  in  the  whole 
of  American  medical  literature  up  to  1914. 

In  describing  the  effects  of  these  bodies  the  three — benzene,  toluene, 
and  xylene — may  be  treated  together,  since  they  differ  only  in  degree. 
Toluene  is  benzene  with  one  methyp,  CHg,  group  taking  the  place  of 
one  H  atom  in  the  benzene  ring,  and  xylene  has  two  such  groups. 
The  entrance  of  the  methyl  group  lessens  toxicity  and  xj^ene  is  said 
to  be  distinctly  less  poisonous  than  benzene,  but  the  difference  be- 
tween benzene  and  toluene  is  not  great;  in  fact,  there  are  experi- 
menters who  claim  to  have  found  toluene  the  more  toxic  of  the  two. 
These  bodies  are  poisonous  to  the  central  nervous  system,  producing 
loss  of  consciousness,  lowered  temperature,  and  disturbance  of  res- 
piration and  pulse  rate.  In  mild  cases  there  is  a  condition  resembling 
early  alcoholic  intoxication,  with  excitement,  pleasurable  or  com- 
bative, headache,  and  dizziness.  This  is  followed  by  depression,  a 
feeling  of  general  illness,  loss  of  appetite,  and  nausea,  sometimes 
vomiting.  If  the  exposure  is  greater,  if  the  fumes  are  heavier,  the 
effect  is  very  rapid  and  the  stage  of  excitement  ma}^  take  the  form  of 
acute  delirium ;  the  man  shouts  and  sings  and  may  be  so  unmanage- 
able that  his  would-be  rescuers  find  it  impossible  to  get  him  out  of 
his  dangerous  situation  before  it  is  too  late.  Loss  of  consciousness 
succeeds  the  delirium.  The  respiration  is  rapid  and  shallow,  the  pulse 
weak  and  rapid,  and  convulsions  may  precede  death.  A  more  exces- 
sive exposure  may  cause  immediate  collapse  and  death  within  a  few 
minutes,  from  paralysis  of  the  nerve  center  controlling  respiration. 

In  the  manufacture  of  explosives,  chiefly  of  picric  acid  from  car- 
bolic acid,  which  in  its  turn  was  made  from  benzene,  there  were 
during  a  year's  time,  1915-16,  14  serious  cases  of  industrial  benzene 
poisoning  officially  reported,  seven  of  which  were  fatal.  All  of  these 
but  two  were  men  who  were  employed  in  some  unusual  piece  of  work — - 
pipe  fitting,  rei^airing  stopcocks,  cleaning  stills  and  tanks.  Germany 
has  had  a  similar  experience.  The  German  factory  inspection  reports 
for  almost  every  year  mention  cases  of  severe  or  fatal  poisoning  from 
benzene  in  men  who  were  repairing  or  cleaning  benzene  receptacles. 
These  cases,  however,  are  rare,  and  so  are  the  British  cases.  We  have 
still  in  the  United  States  an  excessively  large  number  of  deaths  from 
benzene  poisoning,  and  a  study  of  the  records  shows  that  in  some  in- 
stances the  necessary  precautions  are  still  slighted  in  spite  of  the 
growing  number  of  casualties. 

=  For  those  unfamiliar  with  these  chemical  terms  a  short  description  is  given  in  the 
appendix  of  the  structure  of  the  benzene  ring  and  the  principal  derivatives  of  the  ring, 
an  explanation  of  isomeric  forms,  etc.  The  author  is  much  indebted  to  Dr.  W.  Kritchewsky, 
of  the  Sunbeam  Chemical  Co.,  Chicago,  for  his  assistance  in  preparing  the  chemical  parts 
of  this  report. 


BENZENE,  TOLUENE,  AND  XYLENE.  9 

If  the  poisoning  takes  place,  not  through  a  single  exposure  but 
through  repeated  exposures,  the  action  of  benzene  is  characteristic 
and  easily  recognized.  It  acts  on  the  blood-forming  organs,  espe- 
cially the  marrow  of  the  bone,  and  as  a  result  there  is  a  fall  in  the 
number  of  both  red  cells  and  white  cells.  In  one  of  the  cases  de- 
scribed by  Selling,^  of  Baltimore,  the  red  cells,  just  before  death, 
numbered  only  640.000  and  the  white  cells  600.  This  was  in  a  girl 
of  14  Avho  had  been  using  a  cement  of  rubber  and  benzene  to  seal 
cans.  Harrington,*  of  Massachusetts,  reported  five  cases  of  chronic 
benzene  poisoning  in  rubber-boot  makers.  One  of  these,  a  man  who 
had  worked  for  11  m.onths,  died  in  coma  with  convulsions.  Before 
death  the  red  cells  had  fallen  to  1,616,000  and  the  whites  to  850.  The 
second  striking  effect  of  benzene  is  on  the  capillary  blood  vessels, 
Avhich  rupture,  allowing  blood  to  escape  under  the  skin  and  from 
the  mucous  membranes.  The  skin  is  covered  v/ith  purplish  spots 
like  bruises,  there  is  bleeding  from  the  gums,  sometimes  severe  nose- 
bleed or  hemorrhage  from  stomach  or  intestines,  and  in  girls  men- 
strual hemorrhage. 

The  tissues  attacked  by  benzene  are  those  which  must  be  depended 
upon  for  the  production  of  the  so-called  antibodies  which  defend 
the  body  against  infection  by  the  germs  of  disease.  As  a  consequence, 
poisoning  by  benzene,  and  to  a  less  extent  by  toluene,  lowers  the  re- 
sistance to  infections.  In  animals  injection  of  benzene  has  been 
shown  to  favor  the  development  of  an  acute  infection  and  also  the 
lighting  up  of  a  latent  infection.  This  fact  is  of  great  importance 
in  connection  with  industrial  poisoning  from  benzene. 

The  susceptibility  to  benzene  poisoning  varies  very  much,  a  fact 
which  must  be  borne  in  mind  in  connection  with  industrial  cases. 
Not  long  ago  a  report  was  made  on  the  death  of  a  pipe  fitter  from 
benzene  fumes.  The  man  was  changing  coils  in  a  benzene  tank  which 
had  been  thoroughly  blown  out  with  steam  before  he  entered.  There 
was  another  man  in  the  tank  with  him  who  was  not  affected,  and 
the  company  doctor  t'herefore  insisted  that  it  was  the  physical  condi- 
tion of  the  former  that  really  caused  his  death.  In  a  way  that  was 
true;  oversusceptibiiity  to  poison  is  certainly  a  physical  condition, 
yet  no  one  would  think  of  giving  such  an  explanation  for  the  deaths 
from  typhoid  fever,  which  occur  as  a  result  of  drinking  infected 
water,  although  there  are  always  a  large  number  of  people  who  have 
drunk  the  same  water  and  yet  escaped  an  attack  of  typhoid  fever. 
Individual  susceptibility  plaj^s  just  as  large  a  part  in  epidemics  of 
infectious  disease  as  in  poisoning  from  compounds  used  in  industry. 
An  instance  of  the  varying  resistance  to  benzene  is  related  by  the 
manager  of  a  coke  by-products  plant.  There  was  an  overflow  of 
benzene  through  some  accident,  and  two  men  w^ho  were  working  in 
the  room  collapsed  and  fell  in  a  faint.  Two  others  who  went  in  to 
rescue  them  were  also  overcome,  and  so  were  two  more.  After  the 
six  men  had  collapsed,  there  was  a  panic  among  the  other  workmen, 
but  finally  an  Italian  offered  to  go  in,  saying  that  he  never  minded 
the  fumes.  He  did  go  in,  not  even  protected  by  a  helmet,  and  dragged 
out  the  six  men,  one  after  the  other,  himself  apparently  quite  unaf- 
fected by  the  benzene.    Plainly  it  would  be  unfair  to  take  the  Italian 

3  Selling,  L.     Johns-Hopkins  Hospital  Bullclin.      1910,  XXI.  33. 

*  Harrington,    T.    F.     Boston   Medical   and    Surgical    Journal.      1917,    CLXXVII,    203. 


10  IXDUSTRIAL  POISOXIXG  IX    MAKIXG   COAL-TAS   DYES. 

as  the  normal  type :  indeed,  his  lack  of  susceptibility  was  a  deviation 
from  the  normal. 

In  the  manufacture  of  dyes  the  only  cases  of  benzene  poisoning 
so  far  reported  hare  been  of  the  acute  type,  resulting  from  a  single 
exposure  to  more  or  less  hea-vy  fumes.  One  instance  will  be  suiiicient 
to  illustrate  this  sort  of  accident,  for  all  the  reports  read  very  much 
alike.  A  man  was  sent  to  the  top  of  the  benzene  washer  to  change 
the  piping  on  the  spray  nozzle.  He  was  told  not  to  go  into  the 
washer,  which  was  empty  but  had  not  been  cleaned.  He  ignored  this 
order,  took  off  the  manhole  cover,  placed  a  ladder  down  into  the 
washer  and  went  in.  one  of  his  helpers  following  him.  The  momicnt 
he  got  to  the  bottom  of  the  ladder  he  felt  that  he  was  going  to  faint, 
started  to  climb  up,  but  would  have  fallen  if  two  helpers  above  had  I 
not  caught  him  and  dragged  him  out.  As  they  did  so  they  saw  the 
other  man  fall  on  the  bottom  of  the  washer,  but  they  were  obliged 
to  help  the  pipe  fitter  down  from  the  washer  before  they  could  return 
for  the  helper,  and  by  the  time  they  got  him  out  he  was  dying. 

In  this  case  no  attempt  had  been  made  to  render  the  washer  safe 
because  the  man  was  not  supposed  to  go  in.  but  there  are  repeated 
instances  recorded  of  severe  and  even  fatal  poisoning  in  men  who 
have  not  been  allowed  to  enter  the  tank  or  still  until  it  has  beei 
emptied  and  steamed  out  repeatedly.  Even  a  helmet  of  the  Draeger 
type  is  not  always  sufficient  for  protection.  Xot  long  ago  a  man  who 
wore  one  of  these  helmets  fainted  inside  th^  tank  and  died  soon  after 
he  was  removed.  The  onlj  explanation  that  could  be  offered  wa 
that  the  helmet  had  not  entirely  prevented  him  from  breathing 
through  his  nose. 

Several  cases  on  record  in  Germany  show  how  dangerous  may  b( 
the  work  of  cleaning  and  repairing  receptacles  that  have  held  ben- 
zene. Lewin^  in  1907  reported  a  case  of  fatal  poisoning  in  a  work- 
man who  had  tried  to  rescue  a  man  overcome  with  benzene  fumes 
A  benzene  kettle  had  stood  empty  for  22  hours,  then  it  was  washec 
otit  three  times  with  cold  water  and  twice  with  steam  and  wa: 
allowed  to  stand  all  night  filled  with  cold  water.  The  man  who  wa 
sent  in  to  make  repairs  took  with  him  a  pipe  through  which  was  blow- 
ing a  strong  current  of  compressed,  air.  Xevertheless,  he  fainted  anc 
fell  to  the  bottom  of  the  kettle.  Several  men  tried  to  get  him  out 
btit  all  grew  dizzy  and  confused  and  had  to  give  up,  when  an  engi- 
neer, with  a  diver's  helmet  succeeded  in  dragging  him  out.  He  was 
revived,  but  one  of  the  men  who  had  tried  to  rescue  him  died  10 
minutes  after  climbing  out  of  the  kettle. 

The  German  f actorv  inspection  report  for  1913  contains  an  account 
of  a  sunilar  case.  Etere,  also,  the  tank  was  supposedly  thorotighly 
cleaned,  for  it  was  boiled  out  three  times,  but  the  workman  who  went 
in  lost  consciousness:  and  although  the  two  men  who  had  been  se 
to  watch  him  dragged  him  otit  promptly  he  never  came  to. 

There  is  far  less  fatal  benzene  poisoning  in  Great  Britain  than  i 
the  United  States,  and  one  explanation  for  this  fact  was  giv^n  b 
the  manager  of  a  dye  worlds.  He  said  that  it  was  not  safe  to  sen 
a  man  into  a  benzene  tank  or  still,  no  matter  how  carefully  it  had 
been  cleansed,  till  it  had  aired  out  for  fully  two  days,  for  accidents 
were  very  likely  to  occur  if  the  men  were  allowed  to  enter  at  once. 

°  Lewin.     ITiincliener  nie'diziiiiiJctie  Wochenscbrift.      1907,   LIY.  2.377. 


BEliTZENE,   TOLUENE,   AND    XYLENE.  H 

Pie  believed  that  the  metal  absorbs  benzene  and  this  must  first  be 
allowed  to  evaporate. 

The  use  of  solvent  naphtha,  which  is  really  an  impure  mixture  of 
toluene  and  xylene,  in  making  naphthionic  acid  and  in  making  ben- 
zidin,  provides  another  source  of  poisoning  from  these  coal-tar  dis- 
tillates. Naphthalene  is  nitrated  with  Chili  saltpeter  and  sulphuric 
acid,  then  the  nitronaphthalene  is  reduced  with  iron  fillings  and 
hydrochloric  acid  and  the  resulting  alphanaphthylamine  is  removed 
from  the  iron  sludge  with  the  aid  of  solvent  naphtha  heated  with 
steam.  The  naphtha  is  later  recovered  for  further  use  by  distilla- 
tion. In  one  method  of  benzidin,  and  tolidin  production^  reduction 
is  brought  about  by  zinc  dust  and  solvent  naphtha. 

BENZENE  DERIYATIVESo 

The  most  important  compounds  used  in  the  manufacture  of  dyes 
are  derivatives  of  benzene.  The  number  and  complexity  of  tliese 
compounds  is  very  bewildering  to  the  ordinary  investigator,  but  it 
is  not  necessary  that  he  should  be  familiar  with  all  of  them  in  detail, 
because  their  action  on  the  human  body  is  much  the  same,  althougli 
it  is  modified  somewhat  by  differences  in  chemical  structure.  The 
following  is  a  brief  statement  of  what  is  knov/n  as  to  the  relation 
of  chemical  constitution  to  physiological  action  in  the  coal  tar  or 
aromatic  series.^ 

The  phenols  are  hydroxy  (HO)  derivatives;  for  instance,  carbolic 
acid  is  hycJroxj^-benzene;  cresol  is  h3'^droxy-toluene ;  naphthol,' hy- 
clroxy-naphthalene.  The  entrance  of  this  hydroxy  nucleus  renders 
the  naphthols,  alpha  and  beta,  more  irritating  in  their  effect  than 
is  naphthalene.  An  increase  in  the  number  of  hydroxy  groups  in- 
creases toxicity,  thus  p3^rogallol,  trihydroxybenzene,  is  stronger  tha,n 
phenol,  commonly  called  carbolic  acid,  v\^hich  is  monohydroxy  ben- 
zene. But  phenol  is  not  nearly  so  dangerous  an  industrial  poison 
as  benzene,  for  it  is  far  less  volatile.  Severe  burns  may  be  caused 
by  phenol,  although  even  this  is  not  common,  but  systemic  poison- 
ing is  practically  unknown  in  industi*y. 

Pyrogallol,  commonly  called  pj^rogallic  acid,  is  used  in  at  least 
one  plant  in  the  United  States  to  produce  gallocyanine.  German 
reports  tell  of  poisoning  by  this  compound,  but  no  such  case  has  as 
yet  come  to  light  in  this  country. 

The  entrance  of  the  sulphonic  group  (SOgHO)  into  a  benzene  de- 
rivative removes  toxicity,  thus  anilin  is  rendered  harmless  by  sul- 
phonation,  so  is  phenol.  The  entrance  of  COOH  often  has  the  same 
effect ;  nitrobenzoic  acid  is  harmless,  although  nitrobenzene  is  very 
poisonous.  The  acetyl  group  (COCH3)  lessens  toxicity;  acetanilid 
is  less  poisonous  than  anilin.  The  introduction  of  an  alkyl  grouj), 
methyl  (CH3)  or  ethyl  (CoH^)  lessens  toxicity,  dimethylanilin  be- 
ing less  poisonous  than  anilin.  This  is,  however,  only  when  the 
replacement  is  in  the  side  chain,'^  taking  the  place  of  H  in  the  NH2 
group.  If  the  replacement  takes  place  within  the  ring,  toluidin  is 
formed,   which    is    quite    as   toxic    as    anilin.     The    toxicity    of   the 

°  Praenkel,  Sigmnnd.      Die  Arzneimittel  Synthese  auf  Grundlage  der  Beziehun;;-  zvriscbcn 
cbeinisclier  Aufbau  und  Wirkung,  Berlin,   1912. 
■^  See  Appendix  for  an  explanation. 


12  IXDUSTEIAL,   POISOiaisG   I^v'    MAKING   COAJL-TAH   DYES. 

diamines  is  greater  than  that  of  compounds  with  a  single  amine 
(XHg)  ;  phenylendiamine  is  more  toxic  tlian  anilin. 

Chlorine  entering  an  aromatic  compound  changes  it  very  little, 
certainh^  does  not  increase  its  toxicity,  in  fact,  chlorbenzene  seems 
to  be  less  toxic  than  benzene.  The  nitroso  group  (XO)  and  the 
nitro  group  (XOo)  increase,  toxicity  always  whether  they  enter  the 
ring  or  a  side  chain.  All  aromatic  compounds  with  nitrogen  are 
more  toxic  than  those  without,  but  there  is  no  rule  as  to  increas- 
ing toxicity  with  an  increasing  number  of  NO,  groups.  For  in- 
stance, the  1-2-4  isomer  ^  of  clinitrophenol  is  much  more  poisonous 
ihan  trinitrophenol  (picric  acid).  Mononitrobenzene  is  more  poi- 
sonous to  the  central  nervous  system  than  dinitrobenzene,  but  the 
latter  has  a  more  destructive  action  on  the  blood. 

There  is  no  rule  as  to  the  toxicity  of  the  polymerides,  but  usuall}", 
according  to  Fraenkel,'^  the  para  position  is  more  toxic  than  the 
ortho.  This  is  the  general  opinion  of  practical  men  with  regard  to 
ortho  and  para  toluiclin,  the  latter  of  which  is  generally  regarded  as 
much  more  troublesome.  Usually,  paranitranilin  is  considered  more 
dangerous  than  meta,  and  ortho  less  dangerous,  but  animal  experi- 
ments carried  on  by  Lewis,  of  the  Sprague  Memorial  Laboratory 
in  Chicago,  showed  that  for  rabbits  meta  was  more  toxic  than  para. 
In  the  case  of  the  nitrochlorbenzenes  the  ortho  isomer  stands  at  the 
head,  then  the  para,  and  last  the  meta.  As  to  the  phenylendiamines, 
there  is  a  great  difference  of  opinion  among  the  men  in  the  dye 
industry,  some  holding  that  the  para  i^osition  is  the  worst,  others  the 
meta. 

Substitution  j^roducts  formed  by  replacement  of  the  liydrogen  of 
the  ring  are  decidedly  more  toxic  than  substitution  products  formed 
by  replacement  of  the  hydrogen  of  a  side  chain.  The  toluidins  are 
very  toxic ;  benzylaiAine  is  harmless. 

The  physiological  effect  of  the  nitro  and  amido  derivatives  pro- 
duces, in  general,  much  the  same  clinical  picture,  difiering  in  some 
details  and  with  a  few  striking  exceptions.  According  to  Cursch- 
mann  ^  there  is  an  important  difference  between  the  nitro  and  amido 
compounds  in  that  the  latter  are  simply  blood  poisons  and  all  of  the 
symptoms  produced  by  them  may  be  referred  to  their  action  on  the 
blood,  while  the  nitro  compounds  have  in  addition  a  direct  action  on 
the  central  nervous  system.  That  this  is  true  with  regard  to  the 
nitro  compounds  is  undeniable,  but  according  to  Heubner  ^  it  is  true 
of  all  the  benzene  derivatives,  the  amido  as  well  as  the  nitro.  Heub- 
ner succeeded  in  his  experiments  on  rabbits  in  producing  a  narcotic 
effect  with  collapse  and  paralysis  before  blood  changes  had  had  time 
to  take  place,  and  he  holds  that  not  only  nitrobenzene  but  phenol 
and  anilin  affect  the  lower  centers,  those  of  respiration,  vasomotor 
control,  and  heat  regulation. 

In  a  light  case  of  poisoning  from  one  of  these  aromatic  compounds 
the  face  is  flushed,  there  is  a  sense  of  fullness  and  throbbing  in  the 
head,  burning  in  the  throat,  tightness  in  the  chest,  then  a  violent 
throbbing  headache  comes  on,  with  dizziness,  roaring  in  the  ears, 

«  Fi-aenkel,  Sigmund.  Die  Arzneimittel  Synthese  aiif  Grundlage  der  Beziebuns  zwischen 
themischer  Aufbau  und  Wirkung.  Berlin,   1912. 

"  See  Appendix  for  an  explanation. 

^  Curschmann.  F.  Deutsche  Vierteljahrssclirift  fiir  oficentliclie  Gesundheitspflege,  1911. 
XLIII,  22.5. 

'•"  Heubner.     Zentralblatt  fiir  Gewerbehygiene,  1914.      II,  409. 


BENZENE   DERIVATIVES.  13 

and  some  disturbance  of  sight.  The  flushing  of  the  face  subsides 
and  the  color  becomes  livid,  with  bluish  lips  and  tongue,  while  the 
whites  of  the  eyes  are  often  tinged  with  yellow.  If  prompt  treat- 
ment is  given,  which  means  removal  from  all  contact  with  the  poison, 
the  attack  may  last  only  a  fev/  hours,  and  the  man  is  able  to  return 
to  work  on  the  following  day.  But  even  in  so  mild  a  case  as  this  the 
bluish  color  of  the  lips  and  tongue  may  persist  for  several  days.  In 
severer  cases,  the  color  of  the  face  is  gra3-blue,  the  lips  and  tongue 
more  deeply  cyanosecl,  the  muscles  tremble,  the  man  staggers  and 
feels  as  if  his  knees  were  caving  in.  Pie  is  nauseated  and  may  vomit 
and  complain  of  cramps  in  the  abdomen  and  extreme  weakness. 
Sometimes,  usually  a  few  hours  after  the  onset  of  the  attack,  con- 
sciousness is  lost.  The  respiration  is  shallow  and  quick :  the  pulse  is 
small,  fluttering,  irregular,  and  enormously  accelerated;  the  skin  is 
cold  and  the  blood  pressure  is  usually  low.  If  coma  persists  the 
respiration  and  pulse  grow  slower  and  slower,  there  is  involuntary 
defecation  and  urination,  and  convulsions  usually  occur  just  before 
death.  It  is  a  characteristic  feature  of  all  these  poisons  that  the  at- 
tack seldom  takes  place  while  the  man  is  at  work,  almost  always 
while  he  is  on  his  way  home,  or  even  some  hours  later. 

Blood. — Many  studies  have  been  made  of  the  blood  in  poisoning 
from  benzene  derivatives,  and  the  changes  in  acute  intoxication  seem 
to  occur  in  the  following  order.  Methemoglobin  is  formed  early  in 
the  course  of  intoxication,  and  probably  coincidently  with  it  is  a 
destruction  of  red  blood  cells.  (Curschmann,^  Lehmann,^°  Mohr.") 
The  blood  count  and  the  hemoglobin  fall.  Microscopic  examination 
shows  that  the  red  cells  are  altered  in  size,  shape,  and  staining  prop- 
erties. The  cells  are  pale,  there  is  some  fragmentation  and  poly- 
chromatophilia  (abnormal  reaction  to  staining  fluid).  Early  in 
the  attack  the  blood  becomes  chocolate  colored  and  thicker  than  nor- 
mal, and  spectroscopic  examination  may  reveal  lines  which  are  said 
to  be  those  of  methemoglobin  (Mohr^^),  or  rather,  lines  situated 
betvfeen  the  methemoglobin  and  the  oxyhemoglobin,  and  therefore  not 
quite  typical  (Price- Jones  and  Boycott,^^  Brat^^).  If,  however, 
the  spectroscopic  test  is  not  made  till  later  in  the  attack,  it  is  usually 
impossible  to  detect  these  lines.  Indeed  Curschmann  sa5rs  that  by 
the  time  cyanosis  is  fully  developed  methemoglobin  can  no  longer 
be  demonstrated. 

The  evidence  of  the  destruction  of  red  corpuscles  is  succeeded  in 
a  few  days,  from  the  second  to  the  fifth,  by  evidence  of  active  re- 
generation, and  the  blood  picture  then  may  be  very  much  like  that 
of  pernicious  anemia,  with  variations  in  staining  and  in  size  and 
with  the  appearance  of  stippled  cells  and  nucleated  cells.  The 
changes  in  the  white  cells  are  not  so  characteristic,  but  during  an 
acute  attack  there  is  usually  a  polymorphonuclear  leucocytosis. 
Later,  as  also  in  chronic  poisoning,  there  is  a  lessened  number  of 
these  cells  and  a  relative  increase  of  lymphocytes   (Hudson  ^^).     In 

^  Curschmann,  F.  Deutsche  Vierteljahrsschrift  fiir  offentliche  Gesundheitspflege.  1911. 
XLIII,   225. 

'»  Lehmann,  K.  B.     Archiv  fiir  Hygiene.      1912.     LXXV,  1. 

1^  Mohr.     Deutsche  medizinische  Wochenschrift.      1902.     XXVIII,   7.3. 

13  Price-Jones  and  Bo.vcott.     Guy"s   Hospital   Reports.      1901.     LXIII,   309. 

13  Brat.     Deutsche  medizinische  Wochenschrift.     1901.     Nrs.  19  and  20. 

1*  Hudson,  W.   G.     Medical  Record.      1917.     XCI,   89. 


14  IXDUSTEIAL   POISOXIXG   IX    MAKIXG    COAL-TAK   DYES. 

the  sioTver  iorms  of  poisoning  the  destruction  of  red  cells  acts  as  a 
stimulus  to  further  cell  production  on  the  part  of  the  'oone  marrow, 
and  an  increased  red  cell  count  may  be  found.  Maiden  ^^  examined 
the  blood  of  13  men  employed  in  a.n  English  factory  where  anilin 
and  nitrobenzene  were  made.  Six  of  the  13  had  a  high  red  cell  count 
with  a  low  hemoglobin,  and  many  imperfectly  developed  red  cells. 
Loss  of  hemoglobin  ran  from  5  to  50  per  cent.  The  ceUs  showed 
great  variations  in  size,  the  large  predominating,  but  more  note- 
worthy was  the  appearance  of  stipx^led  cells,  which  Maiden  considers 
quite  as  characteristic  of  the  early  stages  of  anilin  poisoning  as  it  is 
of  lead  poisoning.  Maiden  summarizes  the  changes  in  the  blood 
caused  by  small  repeated  doses  of  anilin  thus:  Ked  cells  increased 
in  number  with  loss  of  hemoglobin ;  low  color  index ;  degeneration 
and  imperfect  regeneration  of  red  cells,  increase  of  lymphocytes, 
decrease  of  pol;^Tnorphonuclear  leucoc^'tes. 

U'-noie. — Very  varying  results  are  reported  from  the  analj'sis  of 
the  urine  in  cases  of  acute  poisoning.  Hay  ^  produced  symptoms  in 
liimself  of  intoxication  with  marked  cyanosis  by  rubbing  dinitro- 
benzene  on  his  skin,  but  his  urine  showed  no  abnormality.  Sugar 
and  casts  are  commonly  absent  in  the  urine,  although  there  are  oc- 
casional instances  of  reduction  of  Fehling's  solution.  Albumen  is 
usually  not  found,  except  f>erhaps  for  a  trace,  in  acute  intoxication 
of  moderate  degree,  even  when  the  urine  is  a  dark  brown  color. 
This  brown  color  is  very  common  and  is  often  the  first  warning  the  • 
workman  has  that  he  is  beginning  to  experience  the  effe<;ts  of  the 
poison.  A  chemist  who  once  had  had  a  severe  attack  of  anilin 
poisoning  from  drawing  a  quantity  into  his  mouth  while  siphoning, 
told  me  that  always  after  that  if  he  came  in  contact  with  anilin  he 
would  notice  this  change  in  the  color  of  the  urine,  although  he  might 
feel  no  subjective  symptoms  at  all. 

In  severe  i^oisoning  the  urine  may  be  a  dark  brown  or  the  color  of 
port  wine,  or  a  smoky  red,  and  in  such  cases  methemoglobin  or  un- 
changed liemoglobin  or  blood  pigment,  bile  pigment,  hematoporphy- 
rin,  may  be  detected.  Albumen  can  sometimes  be  demonstrated,  but 
not  always,  even  in  severe  cases  (Mohr^^).  Some  observers  insist 
that  bile  pigment  is  never  found  in  the  urine ;  others  that  bilirubin 
can  be  detected  in  the  majority  of  cases.  Mohr  foumd  hydrobiiirubin 
frequently  after  dinitrobenzene  and  chlorbenzene  poisoning.  No 
thorough  study  has  as  yet  been  made  of  the  reduction  of  Fehling's 
solution,  although  the  occurrence  of  this  phenomenon  is  reported 
fairly  frequently.  Six  such  cases  were  described  in  a  personal 
communication  by  Dr.  Kessler,  of  Marcus  Hook,  in  men  who  had 
been  working  with  dinitrobenzene  and  anilin.  Their  urine  was  dark 
brown,  contained  bile  pigment,  and  had  reducing  properties.  A 
seventh  case  was  one  of  fairly  severe  poisoning  from  mononitro- 
benzene. 

Dr.  Sutherland,  of  the  du  Pont  Co..  who  has  some  1=200  men  under 
his  care,  says  that  he  finds  not  infrequently  urines  reducing  Fehling's 
in  men  who  show  signs  of  poisoning  from  nitro  or  amido  compounds. 

MiUler  reported  a  case  of  anilin  poisoning,  in  which  the  urine 
contained  no  sugar,  no  blood,  nor  albumen,  but  had  strongly  reducing 

6  White  and   Hav.      Laiupt.      1901.      II.   .!i82. 

"  Mohr.      Deutsche  medizinische  Wochenschrift.     1902.     XVIII.   73. 

i^  Maiden.     Journal  of  Hygiene.      1007.     VII,  67i'. 


BENZEJS-E   DERIVATIVES.  15 

properties.  According  to  von  Jaksch,''^  a  substance  which  reduces 
copper  sulphate  and  is  also  lasvorotatory  was  found  in  the  urine  of  a 
man  suffering  from  nitrobenzene  poisoning.  Tliis  urine  smelt 
strongly  of  oil  of  mirbane,  contained  a  trace  of  sugar  and  an  increase 
of  ammonia  and  acetone. 

Neubauer^'  saj^s  that  in  severe  anilin  poisoning  anilin  may  be 
found  unchanged  in  the  urine,  but  this  is  rare.  Usually  it  is  changed 
by  oxidation  and  conjugation  to  paraamidophenol — sulphuric  ester. 
Nitrobenzene  and  the  nitranilins  are  also  excreted,  as  paraamido- 
phenol, while  the  reduction  product  of  dinitrophenol,  which  appears 
in  the  urine  after  poisoning  from  this  substance,  is  amido  2  nitro  4 
phenol. 

Bladder  tumors. — In  the  early  years  of  the  present  century  the  phy- 
sicians attached  to  the  great  color  works  at  Hoechst  noticed  that 
workmen  in  this  plant  were  to  an  unusual  degree  victims  of  tumors 
of  the  bladder,  sometimes  cancerous,  sometimes  benign.  In  1904 
they  began  to  ask  information  from  18  other  German  dye  works  con- 
cerning the  occurrence  of  bladder  tumors  and  of  inflammation  of  the 
bladder,  cystitis,  and  the  responses  to  these  inquiries  brought  to 
light  38  cases,  18  of  which  were  fatal.  This  report  attracted  great 
attention  and  vras  followed  by  others  from  time  to  time  until,  in  192(), 
the  number  of  known  instances  of  bladder  tumor  in  German  dye 
Avorks  reached  177. 

At  a  meeting  of  industrial  phj'-sicians  in  Germany  in  1913  Leuen- 
berger  spoke  on  this  subject,  pointed  out  the  fact  that  it  was  un- 
doubtedly an  amido,  not  a  nitro  body,  which  must  be  held  responsible 
for  bladder  tum_or  formation  and  urged  the  physicians  attached  to 
dye  works  to  tabulate  their  cases  and  discover  which  v\^ere  the  danger- 
ous departments  and  what  was  the  compound  eliminated  in  the  urine 
that  acted  as  an  irritant  to  the  bladder.  The  answers  to  these  ques- 
tions are  now  appearing  in  the  Zentralblatt  f  iir  Gewerbehygiene. 

Schwerin,  of  the  Hoechst  factory,  studied  the  histories  of  99  of 
the  177  cases  and  found  that  they  were  distributed  in  the  following 
departments : 

Cases. 

Fiiclisiii  and  rubiii 21 

Beuzidin  and  uaplithiouic  acid 28 

Naphthylamins 30 

Anilin 8 

Otiier  bases,  not  specified 8 

Palatine  black 1 

Blue 1 

Patent  blue 1 

A  later  report  by  Curschmann  discusses  28  recent  cases — included 
among  the  177 — ox  which  15  were  malignant,  12  benign,  and  one 
mixed.     These  cases  were  distributed  as  follows: 

Cases. 

Fuclisin  and  rubin : 3 

Benzidin  and  naplitliiouic  acid 3 

Betanaphthylamin  and  naplitliol 10 

Anilin  5 

Other    bases 3 

Blue 4 

^°  V.   Jakscli.   R.  Klin.  Diagnostik  innerer  Krankheiten.     6th  ed.     Berlin-Vienna.      1007. 
"  Neubauer.     Analyse  cles  Harns.     11th  ed.     Hupperts's  Lelirbuch.     Wiesbaden.     1913. 
Vol.  2,   1479. 


16  IXDrSTPJAL,   POISOXIXG   IX    MAKIXG    COAL-TAE    DYES. 

The  age  at  which  the  growth  made  its  appearance  was  over  50 
years  for  14  of  the  28,  between  40  and  50  years  for  8,  and  between 
30  and  40  for  6.  The  12  men  who  had  only  benign  tumors  had 
worked  for  a  shorter  time  in  the  industry  than  had  those  with  can- 
cerous growths.  Five  had  been  employed  in  dye  works  for  10  to  15 
years.  5  more  for  15  to  30  years,  and  2  for  more  than  30  years,  but 
of  the  15  with  cancer,  only  2  had  worked  less  than  15  years.  The 
histories  of  many  of  these  cases  show  that  a  tumor  which  is  at  first 
onh'  a  papilloma  may  later  undergo  cancerous  degeneration. 

Curschmann  says  that  although  anilin  may  give  rise  to  these 
tumors  yet  there  is  no  apparent  connection  between  ordinary  anilin 
poisoning  and  bladder  tumors. 

Leuenberger,  at  the  conference  of  industrial  physicians  in  1913, 
expressed  the  view  that  the  amido  compounds  which  seem  to  be  re- 
sponsible for  tumor  growth  in  the  bladder  undergo  hydrolysis  (in- 
troduction of  HO  into  the  ring)  in  the  body  and  suggested  that  it 
might  be  possible  to  ascertain  which  of  the  amido  bodies  are  elimi- 
nated in  this  particular  form,  as  paraamidophenol,  and  then  see 
whether  they  are  actually  the  ones  which  are  associated  with  the 
tumor  cases.  It  is  true,  as  Schmiedeberg  found  years  ago,  that  ani- 
lin and  several  other  aromatic  amido  compounds  are  changed  in 
the  body  to  paraamidox)henol  and  excreted  in  the  urine  as  para- 
amidophenol-sulphuric-ester.  But  this  is  not  true  of  some  compounds 
which  are  apparently  very  important  sources  of  tumor  cases.  Para- 
toluidin  is  one :  others  are  alpha  and  beta  naphthylamin,  both  of 
which  latter  are  excreted  in  the  urine  unchanged. 

Kuchenbacker,  arguing  that  such  a  boclj^  as  paraamidophenol, 
having  a  free  amido  group,  should  be  capable  of  diazotizing  in  acid 
solution  with  nitrate  and  produce  an  azo  color,  tested  the  urines  of 
men  in  a  benzidin-naphthionic  department  and  found  that  those  espe- 
cially of  men  who  were  exposed  to  dusts  produced  a  reddish  azo  dye, 
varying  in  intensity  according  to  the  degree  of  dust  exposure.  He 
could  also  obtain  an  azo  color  from  the  urine  of  dogs  fed  with  anilin, 
and  with  orthotoluidin,  but  not  after  feeding  with  paratoliudin  nor 
with  benzidin,  nor  toliciin,  nor  alpha  nor  beta  naphthylamin. 

It  seems,  therefore,  that  paraamidophenol  is  not  the  only  com- 
pound responsible  for  the  cystitis  and  the  later  papillomatous  tumors 
which  occur  in  these  dye  makers,  and  for  the  present  the  matter 
rests  here.  The  work  of  determining  just  what  does  take  place  in 
the  elimination  of  these  various  aromatic  bodies  and  what  resulting 
compound  sets  up  the  cystitis  which  precedes  tumor  formation  is 
going  forward  in  the  German  laboratories  with  the  hope  that  it  will 
be  possible  some  day  by  means  of  urinary  tests  to  discover  when  such 
a  condition  is  threatened.  ^Meantime  they  have  at  lease  ascertained 
which  are  the  departments  in  which  bladder  difficulties  are  to  be 
looked  for  and  are  in  a  much  better  position  to  guard  against  this 
form  of  occupational  poisoning  than  hitherto. 

In  England  the  dye  industry  is  not  yet  old  enough  to  have  pro- 
duced more  than  a  very  small  number  of  bladder  tum.ors.  The  phy- 
sician connected  with  the  oldest  of  the  English  plants  has  known  of 
two  cases,  although  he  believes  that  there  may  have  been  more 
which  escaped  detection.  Since  only  exceptional  cases  in  Germany 
have  developed  after  less  than  10  years'  exposure,  it  is  highly  im- 


BENZENE    DERIVATIVES.  17 

probable  that  American  dye  works  have  as  yet  been  responsible  for 
anj  cases,  and  our  great  labor  turnover  will  probably  serve  to  protect 
the  greater  number  of  dye  workers  from  it.  However,  skilled  work- 
men and  foremen  and  chemists  are  not  shifting,  and  it  will  be  well 
for  Am.erican  dye  makers  and  industrial  physicians  to  bear  in  mind 
the  German  experience  and  be  on  their  guard  against  similar  occur- 
rences in  their  plants. 

Industrial  poisoning  from  these  compounds,  especially  from  the 
amido  compounds,  is  rarely  fatal.  If  death  occurs  it  is  preceded  by 
coma,  increasing  paralysis  of  heart  and  respiration,  convulsions,  and 
sometimes  edema  of  the  lungs.  These  compounds  do  not  usually 
produce  any  very  characteristic  changes  in  the  organs  with  the  ex- 
ception of  a  few,  such  as,  for  instance,  trinitrotoluene,  which  causes 
a  very  characteristic  degeneration  of  the  liver.  The  usual  findings 
consist  in  slight  degenerative  changes  in  liver,  heart,  and  kidneys 
and  sometimes  pneumonia  or  edema  of  the  lungs,  or  hemorrhages 
into  the  lungs  and  stomach  and  intestines. 

Mode  of  entrance, — The  volatile  compounds  of  this  group  may  be 
inhaled,  but  even  with  the  ^"olatile  compounds  absorption  through 
the  skin  is  more  important,  and  it  is  probably  the  only  mode  of 
poisoning  for  the  solid  compounds. 

The  more  volatile  a  compound  the  more  rapid  the  poisoning. 
Cyanosis  is  greater  in  poisoning  by  amido  derivatives;  the  effect  on 
the  central  nervous  system  is  more  pronounced  in  poisoning  by  nitro 
derivatives.  In  Haj^'s "  experiment  on  himself,  a  few  hours  after  a 
second  application  of  0.1  gram  of  dinitrobenzene  in  ointment  his 
lips  became  a  vivid  blue  color,  his  skin  leaden,  his  pulse  was  120, 
with  high  tension,  and  there  was  a  sense  of  fullness  and  throbbing 
in  his  head.  Curschmann®  produced  fatal  poisoning  from  para- 
nitranilin  in  cats  by  rubbing  a  few  grams  on  the  skin,  and  the  same 
result  was  obtained  with  phen5dene  diamine.  Skin  absorption  is 
favored  bj^  intimacy  of  contact,  pressure,  or  rubbing,  a  hot  atmosphere 
which  flushes  the  surface  blood  vessels  and  causes  sweating,  by  per- 
sonal idiosyncracy  (probably  dependent  on  the  character  of  the 
sweat),  and  finally  by  the  ability  of  the  compound  to  dissolve  fatty 
acids  and  pass  rapidly  through  the  skin. 

Although  there  is  no  doubt  that  skin  absorption  is  very  much  the 
most  important  factor  in  industrial  poisoning,  symptoms  may  also 
be  produced  by  the  inhalation  of  fumes  and  dust,  as  was  shown, 
for  instance  in  the  British  studies  in  trinitrotoluene  poisoning  dur- 
ing the  war.  Most  of  the  TNT  poisoning  in  the  ammunition  works 
followed  direct  contact  with  the  substance,  but  there  was  also  evi- 
dence that  fumes  and  dust  were  not  negligible.  The  same  thing 
was  found  to  be  true  in  American  TNT  manufacture  and  loading, 
where  the  greater  part  of  the  trouble  came  from  contact,  but  fumes, 
especially  when  mixed  with  steam,  gave  rise  to  unmistakable  absorp- 
tion of  the  poison.^®  Several  instances  have  been  reported  of  un- 
complicated fume  poisoning  from  anilin  and  other  compounds  in 

"White   aud  Haj'.     Lancet.     1901.     II,   582. 

^  Curschmann,  F.  Deutsche  Viei-teljahresscbrift  fiir  offentliche  Gesundheitspflege.  1911. 
XLIII,   225. 

Impractical  points  in  the  prevention  of  TNT  poisoning.  Monthly  Labok  Rea'iew, 
United  States  Bureau  of  Labor  Statistics.     January,   1919,  p.  24S. 

25431°— 21 2 


18  IXDUSTEIAL   POISOXINGV   IIST    MAKIiSTG    COAL-TAE   DYES. 

dye  T\-orks.  For  instance,  a  poisoning  occurred  on  the  second  story 
of  a  reduction  building  from  aniiin  fumes  ■which  passed  through  the 
cracks  in  the  wooden  floor  from  the  story  below.  The  apparatus 
"was  very  poor  in  this  reduction  department,  and  it  was  often  neces- 
sary to  open  up  the  reducers  and  dig  out  the  caked  iron  filings,  so 
that  the  fumes  of  aniiin  v/ere  often  quite  heavy.  In  another  case, 
a  man  was  working  a  machine  like  a  cream  separator  for  separating 
aniiin  from  water.  He  did  not  come  in  contact  with  the  aniiin  at 
all,  but  he  was  taken  ill  and  was  under  treatment  for  eight  claj's. 
The  installation  of  a  suction  fan  to  draw  aw^ay  the  fimies  made 
it  i^ossible  for  him  to  go  back  to  his  work  wath  no  further  trouble. 

From  another  plant  conies  the  history  of  a  man  who  Tvas  set  to 
make  repairs  above  a  reducer  where  monochloranilin  was  being  made 
from  nitrochiorbenzene,  Eeduction  was  over  and  fumes  were  com- 
ing off  from  the  hot  open  reducer.  The  man  was  working  at  the 
ceiling  just  over  it,  and  after  45  minutes  he  had  to  be  carried  down, 
overcome  by  the  fumes.  He  was  dangerously  ill  for  several  days, 
and  could  not  return  to  work  for  some  weeks.  Cases  of  fum_e  poison- 
ing also  occur  among  men  engaged  in  centrifuging  (called  "  wring- 
ing" or  "spinning")  the  mixed  toluidins  to  separate  para  crj^stals 
from  the  oily  ortho.  Even  when  the  centrifuges  are  out  of  doors 
very  heavy  fumes  are  given  off  during  the  process  and  apparentbr 
severe  poisoning  may  occur  without  any  contact  at  all. 

The  above  is  a  description  of  tj^pical  poisoning  from  most  of  the 
nitro  and  amido  derivatives  of  benzene.  It  is  necessary,  however, 
to  take  up  the  more  important  compounds  in  greater  detail,  because 
they  differ  from  one  another  more  or  less  with  regard  to  the  promi- 
nence of  one  or  the  other  symptom  and  they  diff'er  in  degree  of 
toxicitj?-,  and  in  at  least  one  instance  (dinitrophenol  1-2-4)  there 
is  a  decided  divergence  from  the  usual  type. 

THE  NITEO  COMPOUNDS. 

Mononiiro'bensene  (CgFIgNOo)  and  metadimtrooenzene  (CrH^ 
(j^Oa),)  ai"©  very  important  in  the  dye  industry.  Mononitrobenzene 
is  a  yellow  oilj"  fluid,  sm^elling  like  oil  of  bitter  almonds,  insoluble 
in  water  but  readily  soluble  in  fats.  It  therefore  passes  easily 
through  the  skin  and  may  cause  poisoning  in  this  way  or  through 
the  inhalation  of  fumes.  In  animals  death  is  brought  about  more 
quickh?-  by  the  liquid  mononitrobenzene  than  by  the  solid  dinitro, 
and  this  is  also  probabl}^  true  in  human  beings.  Occasional!}^  mono- 
nitrobenzene is  spilled  or  splashed  on  the  skin  and  then  the  symp- 
toms of  poisoning  come  on  very  quickly.  The  blood  may  turn  choc- 
olate color  and  the  urine  dark  within  a  few  hours  after  a  slight 
accident  of  this  sort.  If  the  clothing  is  soaked  with  nitrobenzene 
the  resulting  collapse  m.ay  be  very  sudden  and  severe. 

An  account  of  a  fatal  case  of  nitrobenzene  intoxication  ma,y  be 
found  in  the  recorcls  of  the  Massachusetts  General  Hospital  for  July. 
1916.  The  patient,  an  elderly  m.an,  was  at  work  in  a  soap  factory, 
carrying  a  5-gallon  can  of  oil  of  mirbane.  He  seems  to  have  spilled 
some  of  the  fluid  on  his  trousers,  and  was  seen  to  grow  rather  shaky 
and  then  suddenly  collapsed,  spilling  more  of  the  fluid  on  himself. 
It  is  evident  from  the  record  that  his  mirbane-soaked  clothing  was 


THE    I^TITRO    COMPOUi^DS.  19 

not  removed  but  that  he  was  sent  to  the  hosj)tal  as  he  was,  so  that 
it  is  no  wonder  that  b}'  the  time  he  reached  there  his  condition  was 
serious.  He  was  unconscious,  breathing  slowly  and  irregularly,  but 
the  heart  was  regular  with  good  action.  His  pupils  were  small, 
irregular,  and  did  not  react.  The  skin  was  of  a  dark  gi'ay-bhie 
color.  Some  blood  was  withdrawn  from  the  arm  vein  and  it  was 
chocolate  colored.  Respiration  failed,  becoming  more  irregular  and 
shallow,  but  the  heart  action  was  good  till  just  before  death,  which 
occurred  one  hour  after  he  reached  the  hospital. 

Dinitrobenzene  (meta)  is  a  solid,  which,  however,  volatilizes 
slightly  at  room  temperature.  By  universal  agreement  it  is  pro- 
nounced the  most  troublesome  compound  that  is  used  in  anilin-dye 
manufacture.  This  does  not  mean  that  it  is  more  poisonous  than 
mononitrobenzene,  but  that  the  requirements  of  manufacture  are 
such  that  men  are  necessarily  brought  in  contact  with  it  far  more, 
and  therefore  industrial  poisoning  is  much  harder  to  control.  The 
symptoms  of  acute  poisoning  are  the  same  as  those  of  nitrobenzene 
poisoning,  but  in  addition  to  acute  intoxication  there  is  a  more 
chronic  form,  which  has  been  described  by  the  British  and  the 
Germans,  both  of  whom  have  had  ample  opportunity  to  observe  it 
among  the  workers  in  factories  making  roburite,  an  explosive  much 
used  before  the  war,  consisting  of  dinitrobenzene  and  ammonium 
nitrate.  Prosser  White  ^^  describes  a  severe  form  of  anemia  in 
dinitrobenzene  workers,  with  a  dusky  yellow  skin,  jaundiced  sclera, 
an  appearance  of  partial  asphyxia,  wasted  muscles,  dulled  sensi- 
bility, partial  paralysis  of  the  hand,  defects  of  vision.  Dr.  Rox- 
burgli,  of  Manchester,  England,  told  of  a  symptom  he  had  observed 
as  an  aftereffect  of  dinitrobenzene  poisoning  in  two  men,  which 
consisted  in  ataxic  gait,  the  men  staggering  as  if  from  drunkenness. 
This  came  on  intermittently  during  more  than  a  week's  time. 

Rohl  '"^  saw  GO  cases  of  dinitrobenzene  poisoning  in  a  roburite 
factory  at  Y/itten.  The  men  were  emaciated  and  weak,  the  skin 
was  dirty  yellow,  the  pulse  weak,  the  spleen  enlarged,  there  was 
dizziness,  narrowing  of  the  field  of  vision,  and  disturbances  of  sen- 
sation, especially  a  feeling  of  cold  and  weight  in  the  legs.  In  the 
worst  cases  the  blood  was  chocolate  colored. 

In  American  dye  works  DNB,  as  it  is  called,  is  much  dreaded. 
Often  it  is  the  only  substance  that  causes  real  alarm.  There  is  much 
mf)re  exhaustion,  more  weakening  of  the  heart,  than  in  poisoning 
from  anilin,  and  the  effects  of  an  acute  attack  last  much  longer, 
dragging  on  sometimes  for  d^ajs  or  weeks.  The  anemia  may  be 
extreme  and  persistent.  Acute  poisoning  from  a  single  large  dose 
is  exceptional  and  is  usually  the  result  of  an  accident.  In  one  plant 
16  men  were  poisoned,  several  of  them  being  unconscious  for  6  to  8 
hours,  and  one  had  convulsions  at  intervals  for  12  hours.  They 
were  tearing  out  bricks  and  rafters  in  an  old  room  which  had  been 
used  for  the  production  of  DNB. 

It  is  not  only  in  the  production  of  DNB  but  in  its  use  as  an  inter- 
mediate, especially  for  reduction  to  metaphenjdendiamine  and  for 
reduction  to  metanitranilin,  that  the  danger  arises.    Formerh'  DNB 

^^  Prosser  White.     In  Oliver's  Dangrerous  Trades.      London,   1002,  p.  473. 
^"iRohi.     Ueber  akute  uud  chronische  Intoxikationen  durcli  Nitiokorper  der  Benzolreihe. 
Inan.unralions   Dissertation  Rostock,   1S90. 


20  IXDUSTFJ^U.   POISOXIXG   IN    MAKIXG    COAL-TAH   DYES. 

used  to  be  run  out  into  open  pans,  where  it  caked,  and  men  were  sent 
to  choi3  up  the  cake  and  skoyel  the  fragments  into  trucks,  in  the 
course  of  which  work  a  great  deal  of  poisoning  occurred.  One  man 
was  interviewed  in  a  hospital,  where  at  the  end  of  a  week  he  was 
still  somewhat  cyanotic.  He  had  worked  for  nine  days  in  an  open 
shed  breaking  up  and  shoveling  solid  DXB.  On  the  ninth  day 
he  had  a  severe  one-sided  headache  and  was  so  dizzy  that  he  was 
obliged  to  go  home.  The  next  day  he  came  back  to  work,  but  after 
a  little  vrhiie  he  became  very  ill  and  deeply  cjTinosed.  He  was  sent 
home,  but  the  cyanosis  persisted,  and  the  company  sent  him  to  the 
hospital  for  a  week.  Another  man  from  the  same  department  had 
to  be  sent  to  the  hospital  after  only  one  day's  work.  Later  on  this 
method  of  handling  DXB  was  generally  abandoned  because  of  the 
effect  on  the  men,  and  the  molten  DXB  is  now  usually  run  out  to 
meet  a  stream  of  cold  water,  which  granulates  it.  However,  even 
the  shoveling  and  dumping  of  the  granulated  material  may  expose  a 
man  to  stifficient  fumes  to  poison  him.  Before  the  introduction  of 
the  pelleting  method  it  was  fotmd  in  one  plant  that  50  per  cent  of 
all  the  sickness  was  among  the  DXB  men,  although  they  numbered 
only  2i  in  a  force  of  1,500.  A  history  of  27  cases  of  acute  poisoning 
in  men  breaking,  screening,  and  washing  DXB  shows  the  duration 
of  incapacity  was  from  1  to  12  days. 

XitrotoJuenes. — Ortho  and  paramononitrotoluene  (CpH^CHgNOo) 
are  used  to  produce  by  reduction  the  important  intermediates 
ortho  and  paratoluidin.  During  the  war  dinitrotoltiene  (CgHoCHg 
(XOa)^)  was  produced  as  a  stage  in  the  manufacture  of  TXT.  In 
the  dye  industry  it  is  used  for  the  production  of  toluylendiamine. 
According  to  Dambleff-^  and  Jaffe^-  the  ortho  is  the  more  poisonous 
of  tiie  mononitrotoluenes,  at  least  for  animals,  but  neither  ortho  nor 
para  is  as  toxic  as  mononitrobenzene.  They  act  more  slowly  and  ap- 
parently only  upon  susceptible  subjects,  for  many  men  can  handle 
them  with  seeming  impimity.  They  are  absorbed  through  the  un- 
broken skin  and  in  susceptible  persons  they  produce  symptoms  re- 
sembling those  of  nitrobenzene  poisoning.  Zieger-^  says  that  the  pa- 
thology and  symptoms  of  mono  and  dinitrotoltiene  are  the  same,  en- 
largenient  and  tenderness  of  the  liver,  cyanosis,  gastric  disturbance, 
painful,  scanty  urination,  destruction  of  red  blood  cells,  methemo- 
globin.  and  the  symptoms  pointing  to  oxygen  starvation.  There  is  a 
record  of  a  typical  case,  with  cyanosis,  shortness  of  breath,  and  head- 
ache, in  a  man  who  was  sent  into  a  tank  which  had  contained  mono- 
nitrotoluene,  but  which  was  supposed  to  be  quite  clean. 

The  French  committee  on  munition  poisons  found  DXT  toxic  to 
animals,  the  deadly  dose  being  0.5  gram  per  kilogram  of  weight.  A 
marked  effect  on  kidneys  and  liver  was  noted.  DXT  seems  to  differ 
in  its  action  from  TXT  in  several  ways.  Dambleff'  quotes  Zieger  as 
emphasizing  the  eye  symptoms  in  DXT  workers,  a  venous  congestion 
of  the  retina  and  disk.'  Cases  of  multiple  neuritis  have  been  described 
in  DXT  workers  differing  from  anything  observed  as  a  result  of  the 


-1  Dambleff.     Beitrliixe  zur  Kenntniss  der  giftigen  Wirkung  nitriorter  Benzole,   Toluole, 
c      Inaugurrttions  Dif^sprtation  Wiirzhurg.  1908. 

"  Jaiie.     Quoted  bv  Robert.     Lehrbuch  der  IntoxrKatiouen. .   Stuttgart,   1911,  p.  804. 
» Zieger.     Inaugurations  Dissertation  Wiirzburg,   1913. 


THE    ISTITEO    COMPOUIsTDS,.  21 

action  of  TNT.  For  instance,  Hamilton  and  Nixon^*  give  the  fol- 
lowing history  of  an  interesting  case:  The  man  was  a  foreman,  39 
years  old,  wdiose  health  had  always  been  good,  Avith  no  history  of 
family  idiosyncrasy  or  of  alcoholism  or  venereal  disease.  He  had 
worked  for  two  years  in  contact  with  DNT.  At  the  end  of  the  first 
year  he  had  numbness  and  prickling  in  the  feet  v/hich,  after  five 
months,  spread  to  the  knees.  There  was  no  pain,  but  a  sensation  like 
the  prickling  of  an  electrical  current.  He  was  changed  to  outside 
work  and  improved,  but  when  he  went  back  to  the  old  v/ork  the 
numbness  increased  in  feet  and  legs.  Then  his  sight  began  to  fail, 
and  examination  showed  20/40ths  in  the  right  eye,  and  2()/70ths  in 
the  left.  There  was  slight  cyanosis,  anemia,  and  numbness  in  the  tips 
of  the  fingers.  Four  months  later  his  sight  failed  so  that  he  was 
obliged  to  quit  work.  Some  time  after  that,  the  authors  found  the 
sight  to  be  6/200ths  in  each  eye.  The  man  could  find  his  way  about, 
but  could  not  recognize  faces.  His.  physical  condition  was  practically 
normal  except  for  the  loss  of  8  pounds  and  he  complained  of  loss  of 
strength.  Examination  of  the  fundus  showed  well-developed 
atrophy,  with  pale  disk,  some  swelling  of  the  veins,  and  contraction 
of  the  arteries.  Vibration  sense  and  joint  sensibility  w^ere  lost  in  the 
toes;  touch  w^as  impaired  but  not  pain;  there  was  impairment  of 
touch  sense  in  the  fingers.  Coordination  was  impaired  in  the  legs; 
not  in  the  hands.  He  complained  of  a  pulling  up  or  jerking  of  the 
muscles  of  the  legs  like  an  electric  shock.  The  onl}'^  reflex  affected 
was  the  patella,  which  was  diminished.  He  was  anemic,  the  red 
cells  numbering  4,900,000,  hemoglobin  80  per  cent,  whites  8,000,  with 
a  normal  differential  count.  He  improved  under  rest  w^ith  sweating, 
and  10  months  later  had  20/40ths  vision  in  his  right  eye,  20/60ths 
in  his  left.  Another  man  in  the  same  plant  quit  work  at  the  end  of 
six  months  because  of  numbness  in  his  feet  and  swelling  so  that  he 
could  not  put  on  his  shoes.  Two  other  men  complained  of  numbness 
in  the  feet,  with  tingling,  difficulty  in  walking,  and  headache. 

Koelsch  2^,  in  Germany,  and  the  experts  of  the  French  commit- 
tee on  munition  poisons  hold  that  the  poisoning  experienced  in  con- 
nection with  DNT  manufacture  is  due  not  to  the  DNT  itself  but 
to  tetranitromethane  and  perhaps  to  certain  isomers  of  DNT  and 
TNT.  The  pure  substances  they  hold  to  be  very  slightly  toxic. 
Certainly  it  is  true  that  the  worst  place  in  a  nitrating  department 
for  DNT  is  the  centrifuge  for  the  separation  of  DNT  from  other 
products  of  nitration,  and  the  men  engaged  in  such  work  believe 
that  the  oily  liquid  which  separates  off  and  is  rejected  is  the  source 
of  the  trouble. 

The  effects  of  trinitrotoluene  were  closely  studied  during  the 
war.  It  is  a  slowly  acting  poison  and  affects  about  one-third  of  the 
people  who  are  exposed  to  it.  Injury  to  the  bone  marrow  causes  a 
great  destruction  of  red  blood  cells  and  as  a  result  a  hematogenous 
jaundice  develops.  Among  the  British  munition  workers  there  were 
360  known  cases  of  toxic  jaundice  from  TNT  poisoning,  with  96 
deaths.  Much  more  rarely  an  aplastic  anemia  of  extreme  type  de- 
veloped without  the  typical  degeneration  of  the  liver.  Both  forms 
were  found  also  in  American  munition  w^orks.    Trinitrotoluene  is  not 

-*  Hamilton,  Arthur  S.,  and  Nixon,  C.  E.  Journal  of  American  Medical  Association,  1918. 
LXX,  2004. 

"  Koelseh.     Miinchener  medizinische   Wochenschrift,     July  24,   1917. 


22  INDUSTRIAL   POIS02,'I2TG   IX    MAKING   COAL-TAE   DYES. 

used  in  dye  manufaetiire  and  it  is  important  in  this  connection  only 
because  its  method  of  action  has  been  so  thoroughly  studied  that 
the  literature  of  TInT  poisoning  may  serve  as  a  guide  to  us  in  the 
understanding  of  similar  compounds  that  are  used  in  dye  manu- 

Xitropa.iphthalenes  (C^oH^XO.,  C.oHJXO.),,  etc.).— The  nitro- 
iiaphthalenes  hare  been  found  by  German  observers,  Silex^*^  and 
others,  to  have  an  effect  upon  the  eye.  It  is  very  gradual  and  not 
painful,  consisting  in  very  small  transparent  vesicles  on  the  cornea 
which  cloud  it  and  diminish  vision.  Industrially  these  bodies  are 
practically  harmless  because  they  have  a  lovv  volatility  and  slight 
solubilitj'.  In  animals,  Eohl  ^^  found  that  he  could  produce 
methemoglobin  with  nitronaphthalenes. 

Ardsol  (C.5H-CI1..O). — Anisol  is  phenol  with  one  methyl  group 
displacing  the  H  of  the  hydroxyl  group.  Orthonitranisol  is  a  dark 
brown  liquid  of  strong  penetrating  odor.  Dambleflf  ^^  found  that 
he  could  produce  death  in  a  rabbit,  with  hemorrhage  into  the  lungs, 
by  rubbing  into  the  skin  a  quantity  representing  0.5  gram  per 
kilogram.  Trinitranisoi  was  apparently  used  by  the  Germans  dur- 
ing the  war  as  an  explosive;  at  least  it  is  mentioned  among  the 
compounds  studied  by  Koelsch  in  his  inquiry  into  munition  poisons. 
He  found  that  it  seemed  to  cause  no  general  symptoms  but  an  affec- 
tion of  the  skin  to  which  practically  all  workmen  were  susceptible. 
An  eruption  came  on  very  c[uickly  after  only  a  few  hours'  exposure, 
spread  all  over  the  body,  with  very  painful  swelling  of  the  eyes, 
swelling  of  the  lymph  glands,  edema  of  the  skin,  superficial  abscesses 
and  secondary  symptoms  from  the  acute  inflammation. 

The  French  committee  on  munition  poisons  found  dinitranisol  to 
be  one  of  the  two  worst  toxic  compounds  among  those  that  were 
tested  on  animals. 

Dinifrophenol  (C6H3HO(X02)2)- — Before  leaving  the  nitro  com- 
pounds it  is  important  to  mention  one  which  is  used  in  dye  manu- 
facture to  a  limited  extent,  and  is  not  in  itself  important,  but  its 
physiological  action  should  be  studied  in  detail  because  it  differs 
so  radically  from  the  action  of  all  the  other  knoTvn  nitro  deriva- 
tives of  the  benzene  ring  which  have  thus  far  been  studied.  Before 
the  war  this  compound  was  not  known  to  differ  in  any  way  from 
the  others,  but  during  the  war  it  was  manufactured  on  a  large  scale 
in  France  and  entered  into  the  composition  of  the  mixture  used  by 
them  for  loading  high  explosive  shells.  The  enormous  human  experi- 
ment carried  on  in  the  French  munition  plants  showed  this  com- 
pound to  be  possessed  of  striking  peculiarities,  and  it  is  important 
to  call  attention  to  these  because  obviously  it  is  possible  that  other 
nitro  bodies  may,  as  they  come  into  more  extended  use,  prove  to  have 
similar  characteristics. 

The  compound  in  question  is  clinitrophenol,  but  only  one  isomer, 
the  one  having  the  HO  group,  which  changes  benzene  to  j)henol, 
occupying  position  1  in  the  ring,  while  the  two  nitro  groups  occupy 

^  Rohl.  Ueber  akute  und  chronisclie  Intoxikationen  durcli  Xitrokorper  der  Benaolreihe. 
Inauguratioiis   Dissertation    Eostock.     1890. 

'-  Dambleff.  Beitrage  zur  Kenntniss  der  giftisen  Wirkung  nitrierter  Benzole,  Toluole, 
etc.     Inaugurations  Dissertation  Wtirzbure;,  1908. 

-c  Silex.     Beiiiner  kiinisclie  Woclienschrift,  1900,  p.   1191. 


THE    ISTITRO    COMPOUjMDS.  23 

positions  2  and  4.-"  It  is  therefore  loiown  as  dinitrophenol  1-2-4. 
The  method  of  manufacture  used  by  the  French  and  in  two  Ameri- 
can plaints  which  were  manufacturing-  for  the  French  starts  with 
monochlorbenzene,  which  is  nitrated  to  clinitrochlorbenzene.  The 
hydroxide  of  calcium  or  sodium  displaces  the  chlorine  and  then  is 
removed  as  a  soluble  chloride  by  hydrochloric  acid,  leaving  clinitro- 
phenoL  This  -was  used  together  with  trinitrophenol,  picric  acid, 
usually  in  the  proportion  of  40  D^NP  to  60  TNP.  The  French  did 
not  expect  any  serious  trouble  from  occupational  poisoning  in  this 
work  because  they  had  long  been  familiar  with  picric  acid  and  as- 
sumed that  dinitrophenol  would  resemble  it  very  closely.  So  much 
illness,  however,  developed  in  connection  with  the  handling  of 
dinitrophenol  and  exposure  to  fumes  and  dust  that  the  Government 
ordered  a  thorough  inquir}^  into  the  action  of  this  compound,  and 
the  result  of  the  inquir3%  together  with  the  clinical  reports  of  actual 
eases  of  poisoning,  have  been  abstracted  for  American  readers  by 
Eoger  G.  Perkins,^^  of  Western  Eesen^e  University,  consultant  in 
hygiene  of  the  United  States  Public  Health  Service. 

Briefly  stated,  the  essential  facts  are  these :  Three  varieties  of  in- 
toxica.tion  are  described:  First,  mild,  subacute,  which  serves  as  a 
warning  to  the  physician  to  remove  the  workman  from  danger  in 
time.  The  m.an  complains  of  loss  of  appetite,  nausea,  sometimes 
vomiting,  colic,  and  diarrhea.  There  is  general  weakness,  vfith 
headache  and  dizziness  and  moderate  sweating,  especially  &±  night. 
The  tong-ue  is  white  and  furred,  and  there  is  decided  loss  of  weight. 
The  urine  shows  the  presence  of  a  reduction  product,  amido-2-nitro- 
4— phenol,  which  test  is  depended  upon  to  indicate  absorption  of 
dinitrophenol.  The  second  form  is  an  acute  intoxication  v/hich  usu- 
ally is  preceded  by  the  type  just  described.  The  onset  is  sudden,  a 
complaint  of  extreme  weariness  in  the  limbs,  painful  constriction  at 
the  base  of  the  chest,  and  a  burning  thirst.  The  face  is  pale,  with 
slight  cyanosis  of  the  lips.  The  man  svv^eats  abundantly  and  shows 
an  agitation  and  anxiety  which  is  quite  characteristic.  Another  xerj 
characteristic  sign  is  short,  difficult  respiration,  the  difficulty  being 
greater  on  inspiration,  while  in  an  asthmatic  attack  it  is  expiration 
which  is  hardest.  There  is  only  a  slight  rise  of  temperature,  the 
pulse  is  regular  and  the  lungs  usually  clear.  There  is  a  decidecl 
diminution  in  the  c^uantity  of  urine,  and  the  reaction  for  the  detec- 
tion of  the  reduction  product,  known  as  the  Derrien  reaction,  in- 
creases in  intensity.  Eemovai  from  work,  with  a  rest  cure,  is  usu- 
ally followed  by  an  increase  in  the  amount  of  urine  passed  and  a 
rapid  recovery,  but  no  immunity  follows  the  attack,  and  these  men 
require  special  watching.  The  third  form  is  fulminating  intoxica- 
tioli.  This  is  especially  noted  among  alcoholics  or  persons  with 
renal  or  hepatic  troubles ;  death  may  take  place  in  a  few  hours.  The 
onset  is  sudden,  with  an  attack  of  weakness  or,  less  often,  violent 
colics  and  diarrhea.    A  fevs'  hours  later  there  is  fever  up  to  or  over 


HO 

NO2 


NO2 

^8  Perkins,  R.  G.     V.  S.  Public  Health  Reports,  1919.     Vol.  344,  p.  2335. 


24  IXDUSTPJzVL   POISOI^THsTG   IIST    MAKIIS7G    COAL-TAR   DYES. 

40°  C.  (104°  Fahrenlieit),  abundant  sweats  which  stam  the  skin 
yellow,  even  over  the  parts  where  there  has  been  no  exposure  to  the 
chemicals.  There  is  intense  thirst,  the  pupils  are  contracted,  the 
patient  is  frightened  and  excited,  and  there  may  be  partial  or  gen- 
eral convulsions.  This  is  followed  by  unconsciousness,  <!oma,  and 
death  in  a  few  hours.  It  is  the  clinical  picture  of  a  fatal  case  of 
uremia.  The  symptoms  in  the  severe  cases  which  get  well  are  much 
the  same  at  first,  but  the  second  or  third  day  shows  marked  im- 
provement, with  rapid  recovery.  Some  A'ery  rapid  cases  are  de- 
scribed, developing  while  the  workman  was  on  his  way  home.  He  is 
found  somewhere  along  the  road  breathing  with  difticulty,  covered 
with  sweat,  with  a  temperature  of  41°  C.  or  even  43°  C.  (105.8°  or 
109.4°  Fahrenheit),  and  he  dies  before  anything  can  be  done.  Some- 
times there  is  a  rise  of  several  degrees  of  temperature  after  death. 
Urine  obtained  by  catheter  shows  an  intense  Derrien. 

Perhaps  the  most  interesting  feature  of  the  post-mortem  examina- 
tion is  that  no  characteristic  lesions  are  found.  There  may  be  edema 
of  the  lungs,  at  times  a  fatt^^  infiltration  of  the  liver,  but  the  micro- 
scopic lesions  in  the  liver  and  kidney  cells  are  inconstant.  The  blood 
and  organs  always  contain  DNP,  or  its  derivatives,  but  this  is  also 
true  of  the  organs  of  workmen  who  die  from  accidental  causes  while 
employed  on  DXP. 

The  French  experimenters  found  that  the  action  of  dinitrophenol 
1-2-4  is  highly  specific.  Xone  of  the  above  sj^mptoms  are  produced 
by  ortho  or  meta  mononitrophenol  while  paramononitrophenol,  which 
produces  similar  results,  does  so  only  in  heavy  doses  and  transiently. 
The  same  thing  is  true  of  the  1-3-4  isomer  of  dinitrophenol.  The 
other  isomers  have  a  different  effect,  causing  the  formation  of  methe- 
moglobin.  Dinitroplienol  1-2-4  is  a  specific  poison,  causing  in  all 
warm-blooded  animals  an  exaggeration  of  the  heat  radiation  activi- 
ties with  progressive  elevation  of  the  temperature  which  may  rise  to 
45°  C.  (113°  F.)  at  death.  The  basis  of  these  phenomena  is  an 
increase  of  cellular  combustion,  oxidation,  which  has  no  relation 
to  muscular  work,  nor  to  any  action  on  any  special  organ,  nor  to  a 
stimulation  of  the  nervous  system,  for  it  occurs  even  in  cold-blooded- 
animals. 

The  compounds  tested  by  the  French  committee  included  the  nitro- 
toluenes,  the  nitroxylenes,  nitranisols,  nitrophenols,  and  chlorben- 
zenes,  and  they  found  that  the  most  toxic  compound  of  all  was  clini- 
troj)henol  1-2-4,  with  the  corresponding  isomer  of  dinitranisol  com- 
ing next  and  chlorbenzene  last. 

There  were  four  deaths  from  dinitrophenol  1-2-4  in  the  two  Ameri- 
can factories  which  manufactured  melenite  for  the  French.  Three  of 
these,  who  were  handling  the  compound  dry,  developed  symptoms 
very  suddenly  and  died  within  24  hours.  From  the  meager  report 
obtainable  it  seems  that  these  cases  were  like  those  described  by  the 
French.  The  fourth  case,  which  occurred  in  another  factory,  was  not 
tA'pical.  The  man  died  after  an  illness  lasting  several  days,  and 
autopsy  showed  that  he  was  suffering  from  a  toxic  jaundice  such  as 
occurred  in  men  poisoned  by  trinitrotoluene.  It  may  be  that  in  this 
instance  some  other  isomer  was  present,  not  the  1-2-4.  From  a  state- 
ment made  by  Lej'mann  -^  in  1902,  sudden  and  severe  poisoning  may 

'■^  Leyraann.     Vierteljahrsschiif t  fiir  gerichtliche  Medizin,  1902.     Supplement,  p.  3ll. 


THE    NITRO    COMPOUNDS.  25 

develop  in  dye  works  from  the  dinitrophenol  used  in  making  sulphur 
black.  Leymann  describes  three  such  cases.  One  man,  who  had  been 
cleaning  some  Avashing  tanks,  collapsed  suddenly  with  pain  in  his 
chest,  vomiting,  then  fever,  and  convulsions,  and  died  in  two  hours. 
The  second  case  had  a  similar  history.  The  third  is  not  described. 
The  dinitrophenol  used  in  the  making  of  sulphur  dyes  is,  it  is  said, 
the  1-2-4  isomer,  and  certainly  the  history  of  Leymann's  cases  re- 
sembles very  strongly  those  reported  from  the  French  munition 
works. 

It  is  not  likely,  however,  that  poisoning  from  this  compound  should 
occur  in  dye  works  except  as  the  result  of  some  accident,  leakage,  or 
something  necessitating  the  interruption  of  the  process  and  repair 
v>^ork,  for  the  dinitrophenol  that  is  formed  is  not  isolated,  it  is  at 
once  fused  with  sulphur  to  form  sulphur  black,  and  workmen  would 
not  come  in  contact  wath  it  in  the  ordinary  procedure  of  the  reaction. 

ANILIN  AND  OTHER  AMIDO  COMPOUNDS. 

The  symptoms  of  the  amido  derivatives  of  the  benzene  ring  are 
less  serious  than  those  caused  by  the  nitro  derivatives.  While  cyano- 
sis is  deeper  with  an  amido  compound,  it  is  not  accompanied  with 
as  severe  prostration  as  follows  poisoning  with  a  nitro  compound. 
A  case  of  dinitrobenzene  poisoning  does  not  present  as  alarming  a 
color  as  one  of  anilin  poisoning,  but  the  symptoms  of  involvement  of 
the  central  nervous  system,  changes  in  pulse,  respiration,  and  body 
temperature  are  much  more  grave.  Convalescence  is  also  slower. 
Typically  a  case  of  anilin  poisoning  does  not  incapacitate  a  man  for 
more  than.^  a  day  or  two,  although  it  is  a  question  whether  he  should 
be  allow^ecl  to  return  to  work  unless  a  blood  examination  shows  his 
hemoglobin  not  much  lower  than  normal.  But  after  dinitrobenzene 
poisoning  a  workman  is  likely  to  be  ill  for  a  fortnight  or  m^ore. 

A  typical  case  of  anilin  poisoning,  selected  at  random  from  a  large 
number  of  similar  records,  has  the  following  history :  An  Irish  pipe 
fitter,  a  fairly  heavy  drinker,  had  worked  for  two  weeks  in  an  anilin 
reduction  department,  his  v/ork  bringing  him  every  now  and  then 
in  direct  contact  witli  anilin-smeared  apparatus.  He  would  come 
back  from  work  weak  and  tired,  complaining  of  the  fumes  in  the 
plant.  His  wife  said  that  his  face  looked  dusky  and  his  eyes  un- 
natural. He  did  not  complain  of  pain,  but  of  feeling  sick  all  over. 
On  the  fifteenth  night  he  lost  consciousness  and  was  taken  to  the  hos- 
pital. The  hospital  record  reads  :  Skin  all  over  body  steel  gray  color ; 
face,  scalp,  and  hands  blue;  unconscious;  pupils  normal;  sclera  jaun- 
diced ;  respiration  somewhat  labored,  30  to  39 ;  temperature  97.2° ; 
pulse  130  to  140,  shallow;  lungs  norm_al;  heart  normal  in  size  and 
sounds ;  abdomen  normal ;  hemoglobin  75  per  cent ;  urine  dark  brown ; 
albumen.  He  vomited  twice  on  the  first  day,  on  the  second  his  mind 
was  clear,  his  pulse  of  good  quality,  but  still  rapid,  112 ;  respirations 
29 ;  temperature  98.4°  ;  no  albumen  in  the  urine.  By  the  seventh  day 
he  could  be  discharged,  but  on  the  tenth  day  he  was  still  weak  and 
his  sclera  still  jaundiced. 

A  severer  poisoning  results  in  intensification  of  all  these  s^/mptoms. 
A  workman  engaged  in  experimental  work  which  involved  exposure  to 
contact  and  fumes  was  seen  July  24, 1916.    He  was  in  profound  coma, 


26  INDUSTRIAL   POISO:jriXG   IX   ]VIAKI2vJ"G   COAL-TAE   DYES. 

liis  breatiiing  -vvas  stertorous,  and  Lis  piiLe  was  irregular  and  of  very 
poor  Cjuaiity.  He  was  so  cyanosed  that  tlie  skin  over  his  Trhole  body 
was  a  deep  plum  color.  That  morning  at  7  he  had  gone  to  work  feel- 
ing perfectly  well  in  every  way  and,  according  to  the  history  ob- 
tained, he  was  exposed  to  fumes  of  aniiin  for  an  hour  and  forty 
minutes  before  he  began  to  notice  any  sysmptoms  of  depression. 
First  came  throbbing  in  the  head  and  increasing  nausea,  which  he 
thought  were  due  to  the  hot  weather  and  the  poorly  ventilated  room. 
He  next  noticed  palpitation  of  the  heart,  and  then  a  violent  headache 
came  on,  increasing  in  intensity  and  accompanied  by  vertigo.  As  he 
said,  *'I  felt  as  if  I  had  been  standing  on  my  head  for  a  long  time 
and  that  every  ounce  of  blood  in  my  body  had  rushed  to  my  brain." 
Tiie  dizziness  increased  and  he  lost  consciousness  comx:>letely  about 
45  minutes  after  the  onset  of  the  first  symptoms.  He  was  picked  up 
by  the  other  worlnnen  and  hurried  to  the  hospital,  where  oxygen  was 
administered  as  well  as  heart  stimulants,  but  apparently  with  little 
effect.  Th-e  cyanosis  persisted,  the  heart  action  was  very  feeble  and 
rem^ainded  so  for  over  16  hours,  and  he  did  not  regain  consciousn-^ss 
till  the  morning  of  July  25,  a  period  of  about  22  hours. 

A  catheterizeci  specimen  of  urine  obtained  on  admission  showed 
nothing  of  note,  but  a  second  examination  was  made  18  hours  later, 
when  the  urine  was  found  to  be  smolry,  specific  gravity  1.022,  there 
was  a  trace  of  albumin,  no  sugar,  and  the  presence  of  hemoglobin 
was  detected  by  the  Heller  test  and  by  the  Schonbein-Almen  turpen- 
tine-guaiac  test.    This  hemoglobinuria  persisted  for  five  days, 

A  blood  examination  made  on  entrance  gave  normal  findings  in 
all  respects  except  for  a  slight  eosinophiiia,  but  four  days  later  there 
were  stippled  red  cells  and  some  irregularity  in  the  size  and  shape 
of  the  cells.    The  hemoglobin  then  was  To  per  cent.     (Sahli.) 

The  patient  suffered  from  severe  headache  for  five  days  and  com- 
plained of  weakness  and  exhaustion  for  at  least  two  weeks  longer, 
after  which  he  improved  slowb/. 

Friedlander  ^'^  reported  from  the  municipal  insane  hospital  in 
Frankf  ort-on-the-Main  a  case  of  acute  maniacal  delirium  in  a  man  who 
had  loosened  a  rubber  pipe  leading  into  an  aniiin  receptacle  and  had 
received  a  splash  in  the  face  and  mouth,  swallowing  about  a  mouthful. 
He  became  delirious  about  four  hours  later  and  was  brought  to  the 
hospital  in  a  strait  jacket  and  deeply  cyanosed.  His  mania  lasted 
until  the  next  day,  when  he  vras  rational  but  excited.  On  the  third 
day  he  was  still  irritable  and  restless,  his  heart  still  weak  a,nd  rapid, 
but  c^Tinosis  had  vanished,  and  by  the  fourth  day  he  was  mentally 
soimd.  A  similar  history  comes  from  an  American  dye  works.  Tlie 
man  was  a  pipe  fitter  and  was  worlring  at  some  pipe  in  the  ceiling 
over  the  aniiin  reducers.  Suddenly  he  became  maniacal  and  ran 
amuck  over  the  plant,  and  it  was  six  hours  before  he  came  to  himself. 
This  case  was  reported  as  one  of  fume  poisoning,  but  it  seems  pos- 
sible that  the  steam  from  the  reducei-s,  which  does  carry  some  aniiin 
with  it.  had  gradually  soaked  the  ceiling  of  the  room  and  that  in 
working  there  the  m_an's  hands  had  become  saturated  with  it. 

Another  American  case  was  also  attributed  to  fumes  of  aniiin. 
A  foreman  was  seriouslv  affected  bv  heaw  fumes  and  was  sent  to  the 


20  FrwHllander.     NVurologiscbes  Centralblatt,  1900.     XIX,  lo5  and  294. 


AITILIN"   AND   OTHER   AMIDO    COMPOUISTDS.  27 

plant  hospital  and  given  oxygen  inhalations,  whereupon  he  became 
delirious,  and  did  not  recover  from  the  attack  till  the  following 
nioming. 

It  is  recognized  by  American  aniiin  workers  that  long  exposure 
to  this  body  is  likely  to  make  men  irritable,  hard  to  deal  with, 
'"  grouchy,''  and  that  they  are  really  not  up  to  a  full  day's  work. 
Their  appetite  is  likely  to  be  poor  and  they  complain  a  good  deal  of 
headache.  A  chronic  form  of  anilinism  was  described  b}^  an  earl}'" 
German  observer,  Hirt,  as  characterized  by  disturbances  of  sensi- 
bility and  of  the  motor  nerves,  inertia,  headache,  digestive  disorders, 
skin  eruptions,  and  roaring  in  the  ears.  A  few  years  ago  men  ex- 
posed to  aniiin  were  not  infrequently  treated  by  their  phj^sicians 
for  chronic  valvular  heart  disease  because  the  cyanosis,  the  altered 
pulse,  and  the  eomj^laint  of  weakness,  breathlessness  on  exertion, 
palpitation  of  the  heart,  and  indigestion  seemed  to  point  to  such  a 
diagnosis.  A  t3'pical  case  of  this  sort  was  reported  in  1914,  when 
the  importance  of  cleanliness  in  aniiin  work  was  not  generally  Iviiovfn. 
The  man  had  worked  with  aniiin  for  nine  months.  He  complained 
especially  of  muscular  weakness  and  fatigue.  Palpitation  of  the 
heart  came  on  when  he  had  any  unusual  exertion  or  simply  at  the 
end  of  the  day's  work,  and  he  had  frequent  headaches  while  at  v/ork, 
sometimes  severe  and  accomjianied  by  nausea  and  dizziness.  Re 
was  never  cyanosed  and  examination  showed  no  phj^sical  abnormality 
except  a  rapid  pulse,  9-i.  While  the  number  of  red  corpuscles  in  the 
blood  v>^as  increased  to  5,400,000,  the  hemoglobin  was  only  68  per  cent. 
Curschmann  lays  great  stress  on  this  slowly  developing  form  of 
poisoning,  especially  from  the  solid  amido  compounds,  the  result 
of  repeated  tiny  doses,  with  a  cumulative  effect.  He  says  that  in 
typical  cases  the  first  sign  of  this  form  of  chronic  poisoning  is  a  loss 
of  hemoglobin,  and  therefore  a  blood  examination  is  of  great  practical 
importance,  because  any  workman  who  has  lost  from  15  per  cent  to 
20  !>er  cent  hemoglobin  is  facing  the  risk  of  an  acute  attack,  and 
should  be  suspended  from  work.  A  slight  cyanosis  is  likely  to  appear 
at  this  stage,  but  no  typical  microscopic  changes  in  the  blood  till  a 
later  stage.  One  of  his  cases  had  an  almost  typical  neurasthenia,  and 
the  only  thing  that  j^ointed  to  aniiin  poisoning  was  the  loss  of  hemo- 
globin and  a  rise  in  blood  pressure.  Curschmann  found  that  the 
average  blood  pressure  by  the  Eiva-Rocci  in  100  workmen  not  ex- 
posed to  aniiin  was  between  110  and  120,  but  in  men  intoxicated  Avith 
aniiin  it  ran  from  135  to  165.  In  cases  of  pronounced  anemia  with 
C3^anosis  there  may  be  a  rise  of  40  in  pressure,  and  with  it  there  is 
always  a  slowed  pulse,  down  to  48,  In  these  cases  there  is  a  slight 
jaundice  and  the  urine  is  brown. 

Older  men  do  not  endure  exposure  to  these  compounds  so  well  as 
younger  m^en.  Dr.  Raymond  Bugbee,  of  Providence,  has  given  the 
histories  of  two  men,  one  between  50  and  60,  the  other  66  years  old, 
both  of  whom  were  severely  poisoned  with  aniiin  after  no  great  ex- 
posure, and  in  addition  suffered  from  pain  in  the  precordium,  which 
persisted  longer  than  any  other  symptom.  According  to  Dr.  Suther- 
land of  the  du  Pont  Co.  negroes  have  no  immunity  as  compared  with 
whites,  but  suffer  just  as  Intensely  from  just  the  same  symptoms. 
The  fact  that  in  aniiin  workers  ciits  are  likely  to  inflame  and  sup- 
purate and  that  sores  are  slow  in  healing  and  may  go  on  to  abscess 


28  IXDUSTEIAL    POISOXIXG    IX    MAKIXG    COAL-TAR    DYES. 

formation  lias  been   observed  by  men   in  charge  of   anilin  ^vorks. 
(See  Adamson^^.) 

Several  instances  are  on  record  of  an  intercurrent  attack  of  in- 
fluenza affecting  the  course  of  a  case  of  poisoning.  For  instance,  a 
chemist  "who  was  Tvorking  with  metanitranilin  went  home  ill  with 
what  proved  to  be  an  attack  of  influenza.  This  was  on  a  Saturday. 
On  the  following  Tuesday  he  suddenly  developed  an  attack  of 
jaundice  with  cyanosis.  Eelapses,  without  any  further  exposure  to 
the  poison  are  also  related.  A  workman,  31  years  old,  had  had  an 
attack  of  anilin  poisoning  several  months  before  in  another  factory. 
He  was  overcome  in  the  second  factory  on  April  2,  went  home,  and 
apparently  recovered,  but  on  April  5,  while  he  was  still  at  home, 
he  suddenly  became  violently  ill,  lost  consciousness,  and  was  taken 
in  this  condition  to  the  hospital,  where  for  two  hours  he  had  attacks 
of  projectile  vomiting.  Vriien  he  regained  consciousness  he  suffered 
from  headache  and  dizziness.     He  was  in  the  hospital  for  six  days. 

In  the  German  literature  there  are  frequent  references  to  dis- 
turbances of  vision  in  the  course  of  anilin  poisoning,  but  there  is 
no  mention  of  this  complication  in  American  literature,  so  far  as 
the  writer  knows.  An  article  by  Senn^-  deals  with  a  serious  affec- 
tion of  the  eye  among  dyers  in  a  Swiss  factor}^  It  consisted  in  a 
loosening  of  the  epithelial  covering  of  the  cornea,  with  subsequent 
inflammation,  cloudiness,  discoloration,  and  therefore  loss  of  vision. 
This  was  found  among  men  who  were  working  over  vats  of  steaming 
anilin  black,  which  is  essentially  a  mixture  of  anilin  and  hydro- 
chloric acid,  and  Senn  attributed  it  to  the  effect  of  the  oxidation 
products  of  anilin,  the  quinones,  which  cause  a  painful  smarting  of 
the  eyes  so  that  the  man  rubs  them  vigorously  and  detaches  the  sur- 
face cells,  leaving  the  cornea  exposed  to  further  cauterization. 

Toluidins  (CoH^CHgXH,). — The  toiuidins,  ortho  and  para,  are 
considered  by  some  to  be  more  toxic  than  anilin  itself.  Posner  and 
Liebreich"^  say  that  crude  anilin  is  more  poisonous  than  pure  be- 
cause of  the  presence  of  toluidins,  and  von  Jaksch  ^*  makes  the  same 
statement.  Treitenf eld  °^  finds  that  thej^  work  very  much  as  anilin 
does,  having  the  same  effect  on  the  central  nervous  system,  but  caus- 
ing rather  less  cj'anosis,  but  in  a  case  described  by  Starck  ^^  the  man 
was  not  onh'  comatose  for  29  hours,  but  so  deepty  cyanosed  as  to  be 
almost  black.  Eambousek^^  says  that  the  toluidins  act  like  anilin 
but  have  a  stronger  effect  on  the  urinary  system,  causing  strangury 
and  hematuria  more  than  does  anilin,  and  Dr.  Kessler,  of  the  Anilin 
Products  Co.,  says  that  his  experience  confirms  this.  Strangury 
(suppression  of  urine)  is  also  noted  by  Friedliinder  ^°  in  toluidin 
poisoning. 

Gibbs  and  Hare  ^®  tested  the  three  isomers,  para,  ortho,  and  meta 
toluidin,  on  animals,  and  found  that  all  destroy  red  blood  cells,  lower 

3"  Friedlander.     Xeurologisches  Centralblatt,  1900.     XIX.  1.55  and  29-1. 

^1  Adamson,  George.  Journal  of  Industrial  and  Engineering  Chemistrv.  1910.  VIII, 
1058. 

2-  Correspondenzblatt  fiir  Schweizer  Aertze,   1S97.  p.   161. 

^  Posner  and  Liebreich.  Quoted  bv  Robert,  Lehrbuch.  der  Intoxikationen.  Stuttgart, 
1911.     P.   790. 

^  V.  Jaksch.  R.     Die  Vergiftungen.     Vienna,   1012,   p.  325. 

^  Treitenfeld.  Quoted  by  Robert,  Lehrbuch.  der  Intosikationen.  Stuttgart  1911,  p. 
790. 

2«  Starck,  M.     Therapeutische  Monatshefte.     1S92.     VI,  .S76. 

^  Rambousck.  .T.      Industrial  PoisoQin-r.     Translated  by  T.  M.  Legge.     London,  191.T. 

^  Gibbs  and  Hare.     Quoted  by  Kobert,  Lehrbuch  der  Intoxikatioiien.     Stuttgart,   1911. 


anilijSt  and  other  amido  compounds.  29 

the  temperature,  and  lame  the  spinal  cord.  The  fatal  dose  per  kilo- 
gram of  weight  is:  For  para,  0.1  gram;  for  meta,  0.125  gram;  and 
for  ortho.  0.208  gram.  Meta  is  not  used  in  dj^e  manufacture,  and 
most  of  the  Americans  who  have  had  practical  experience  with  para 
and  ortho  confirm  the  statement  of  Gibbs  and  Hare  that  para  is 
more  toxic  than  ortho,  although  it  is  crystalline  while  ortho  is  an 
oiiy  liquid.  One  industrial  physician,  however,  believes  that  ortho 
is  distinctly  more  poisonous  than  para,  because  it  is  more  easily  ab- 
sorbed. In  several  large  plants  the  toluidins  are  said  to  give  more 
trouble  than  the  fumes  of  anilin,  not  necessarily  because  they  are 
more  poisonous  but  because  there  is  not  any  process  in  anilin  manu- 
facture except  repairing  and  cleaning  which  necessitates  as  much 
exposure  to  fumes  and  contact  as  does  the  centrif uging  or  '°  spin- 
ning "  of  the  two  toluidins.  A  man  with  a  case  of  paratoluidin 
poisoning,  chronic,  with  acute  exacerbation,  came  recently  to  the 
occupational  disease  clinic  of  the  Massachusetts  General  Hospital. 
He  had  been  poisoned  by  fumes  from  the  sulphur  fusion  of  para- 
toluidin for  primuline.  He  had  the  symptoms  typical  of  chronic 
poisoning  with  unusually  distressing  breathiessness  on  exertion.  A 
large  plant  reported  seven  cases  of  poisoning  vvitliin  a  short  time  in 
the  research  department  in  men  who  were  separating  ortho  from 
paratoluidin. 

Even  acute  mania  may  develop  as  a  result  of  toluidin  poisoning. 
One  of  the  cases  reported  by  Friedlander  ^'^  was  in  a  man  v«^ho  had  to 
repair  a  toluidin  pump  and  splashed  some  on  his  face  and  chest.  He 
did  not  change  his  clothes,  and  two  hours  later  he  was  found  on  the 
ground  outside  apparently  sleeping.  When  he  was  roused  he  became 
maniacal  and  had  to  be  taken  to  the  asylum.  He  was  cyanosed,  res- 
piration rapid  and  labored,  pulse  very  irregular,  gait  staggering. 
He  was  in  delirium  with  convulsions  for  some  14  hours,  and  his 
mind  was  not  entirely  clear  till  the  third  day  after.  This  case  also 
displayed  the  characteristic  urinary  symptoms,  very  scanty,  painful 
micturition,  only  100  cc,  of  urine  passed,  with  agonizing  pain,  on  the 
first  day.  This  persisted  and  the  quantity  did  not  reach  1,000  cc. 
till  the  ninth  day.  There  was  albumen  in  the  urine,  but  no  blood. 
The  man  was  in  the  hospital  three  weeks. 

Starck's^^  case  is  another  very  striking  one.  The  man  got  his 
clothing  soaked  while  dipping  mixed  toluidins  from  an  open  recep- 
tacle, and  did  not  receive  proper  treatment  till  more  than  24  hours 
later,  so  that  the  poison  had  full  opportunity  to  work.  He  began 
to  feel  the  effect  at  6  in  the  morning — he  was  on  the  night  shift — ^but 
finished  his  shift,  working  on  till  7.  At  11  he  lost  consciousness,  at 
6  that  evening  he  lay  in  coma,  motionless,  eyes  half  open,  mouth 
tightly  closed,  a  little  foam  on  his  lips.  He  was  still  in  his  soaked 
clothing  and  was  given  cognac  as  a  remedy.  The  next  morning  he 
was  extremely  cyanosed,  his  lips  and  mouth  almost  black,  and  there 
was  some  trismus,  but  he  was  conscious,  complaining  of  severe  head- 
ache. His  pulse  was  small,  his  respiration  slow  and  labored,  his 
breath  smelled  strongly  of  anilin,  so  did  the  feces.  Very  severe 
strangury  developed,  the  urine  was  bloody  and  passed  only  in  drops. 
This  increased  until  he  became  delirious  with  the  pain,  and  it  was 

3"  Friedlander.     Neurologisches   Centralblatt.      1900.     XIX,   155  and  294. 
» Starck,  M.     Therapeutische  Monatshefte.     1892.     VI,  376. 


30  TFDUSTEIAL,   POISOI^IITG   11^    MAKING    COAL-TAE   DYES. 

not  till  the  fifth  clay  that  it  lessened,  but  the  urine  remained  blood}'- 
till  the  tenth  day.  'He  had  distress  in  the  abdomen,  great  thirst,  but 
loathing  for  food.  After  all  symptoms  cleared  up  there  remained, 
pronounced  weakness  and  he  was  not  fit  for  work  for  five  weeks. 
The  case  was  undoubtedly  gTeatly  aggravated  by  neglect  and  mal- 
practice. 

Xylidin.  (GcH3(CH3)2NH,).— Very  little  is  written  of  the  action 
of  the  xylidins,  but  they  are  undoubtedly  less  poisonous  than  anilin 
and  toluidin.  Acetyl-para-tokiidin  v/as  found  in  use  in  one  plant, 
and  was  said  to  be  toxic. 

Diamines  {CQJizCA„{l^l\^)^). — The  diamines  are  notoriously 
toxic.  T oluyiendimjiine  has  long  been  regarded  as  a  typical  blood 
poison.  Stadelmann^^  experimented  with  toluAdendiamine  on  dogs 
and  found  extensive  destruction  of  red  blood  corpuscles  and  severe 
hematogenous  jaundice.  Dragendorff*^  found  methemoglobin,  de- 
struction of  liver  cells,  and  a  loss  of  alkalinity  of  the  blood,  which  was 
brownish  black. 

The  two  vhenylend/lamines  {O^A^y'E'H.^) r,) ^  para  and  meta,  are  very 
important  intermediates  in  dye  manufacture.  Para  was  used  as  a 
hair  dye  until  its  dangerous  nature  was  discovered.  It  is  still  used 
for  dyeing  furs,  under  the  name  of  ursol,  and  is  the  cause  of  very 
severe  eczema  with  swelling  of  the  ej^elids  and  sometimes  ulcers  and 
cellulitis  in  fur  dyers  and  even  in  furriers  and  women  who  wear  furs 
dyed  with  this  compound.  When  used  as  a  hair  dj^e  and  rubbed  into 
the  roots  of  the  hair,  paraphenyiendiamine  has  been  known  to  set 
up  not  onl}^  a  dermatitis  but  severe  symptoms  of  nervous  disturbance, 
sleeplessness,  dizziness,  weakness  of  the  legs,  even  epileptiform  con- 
vulsions, loss  of  consciousness,  and  death.  (Knowles  ■*"-.)  According 
to  Blaschko'-,  however,  the  irritating  effect  of  hair  dyes  and  fur 
dyes  containing  paraphenyiendiamine  is  not  caused  by  this  com- 
pound but  by  the  presence  of  a  mid  product,  quinone  dichlordiamine, 
which  has  a  m.uch  more  irritating  effect  on  the  skin.  Olson  ^^  also 
attributes  the  skin  eruptions  to  quinone  dichlordiamine  and  says  that 
when  oxidation  is  complete  phenyiendiamine  is  not  irritating  to  the 
skin.  This  probably  explains  the  contradictory  statements  about 
this  compound,  which  are  made  by  the  men  who  handle  it,  for  in  one 
factory  it  will  be  said  to  give  a  great  deal  of  trouble  from  skin  erup- 
tions and  in  another  it  is  handled  with  no  difficulty  at  all.  Para- 
phenyldiamine  is  also  used  as  an  intermediate  for  sulphur  dyes. 
Criegern^*  has  described  asthmatic  attacks  in  paraphenyiendiamine 
workers  and  the  files  of  the  New  York  Labor  Department  contain  the 
report  of  a  case  of  eczema,  bronchitis,  and  asthma  in  a  man  who 
mixed  ursol  for  dyeing  furs. 

Meta  is  used  as  an  intermediate  for  Bismarck  brown,  Manchester 
brown,  and  many  azo  dyes.  It  causes  skin  eruptions  and  the  steam 
from  filter  presses  is  said  to  cause  systemic  poisoning.  It  is  usually 
considered  more  dangerous  than  para,  but  since  it  is  made  by  the 

•■"^  Stadelmann.      Quoted  l)v  Maiden.      Journal  of  Hygiene,  1907.      VII,  672. 

•">  Di-agendorff.  Quoted  iiv  Robert.  L9hrl)ucli  dei-  Intoxikatior.or..  Stuttgart,  1911, 
p.    7S2. 

"  Knowles.   F.   C.     Medical  Record.  191G,  d.  217. 

•'^  Blaschko.     Deutsche  mediziul.sche  WocheDselirift.  1913,  II.  2400. 

•"•Olson,  G.  M.      Journal  of  American  Medical  Association.  191(i.  LXVI.  8G4. 

^  Criegera.  Quoted  by  Robert.  Lehrbucli  d^'r  lutoxlkatiooeik.  Stuttgart,  19ll,  p. 
05.".. 


AlSriLIaS"   AIs^D    OTHER   AMIDO    COMPOUlsTDS.  31 

reduction  of  dinitrobenz?ene  it  is  quite  possible  that  traces  of  unre- 
duced DNB  may  be  responsible  for  effects  attributed  to  i:)hen3dendia- 
mine. 

Difhenylaraine  {Q.^.-^M'W). — Diphenylamine,  wliicli  may  be 
regarded  as  ammonia  (NHo)  with  two  hydrogen  atoms  replaced  by 
phenjd  (CgH,,)  groups,  is  said  by  Harnack"*"  to  cause  in  cold-blooded 
animals  a  slow  paralysis,  probably  from  chronic  blood  changes. 
Kobert  -®  saj^s  that  warm-blooded  animals  can  tolerate  large  doses, 
but  later  on  they  die  of  marasmas,  although  he  is  uncertain  how  far 
this  is  due  to  the  effect  on  the  blood.  Large  quantities  of  diphenyla- 
mine  were  manufactured  in  the  United  States  during  the  war  and 
dissolved  in  ether  alcohol  with  nitrocotton  and  then  incorporated 
with  the  nitroglj'-cerin  powders.  There  was  no  evidence  of  any 
poisoning  among  the  men  manufacturing  and  packing  diphenyla- 
mine;  and  if  it  had  any  effect  on  the  w^orkers  in  smokeless  powder 
and  mixed  powder  manufacture,  it  was  masked  by  the  other  toxic 
substances — Qther-alcohol,  nitroglycerin,  and  amyl  acetate.  In  dye 
manufacture  diphenylamine  is  used  for  the  production  of  metanil 
yellow  and  azo  3^elIow. 

Nitranllhi  (CgH.j^NHoNOo)  .■ — Of  the  three  isomers  of  nitranilin,  two 
are  important,  para  and  meta.  Kobert  ^^  and  Eambousek  ® '  both  think 
■  that  paranitranilin  is  more  toxic  than  meta.  Gibbs  and  Hare  '^  say 
that  both  cause  formation  of  methemoglobin  and  laming  of  the  central 
nervous  system  and  heart.  They  find  para  the  most  toxic,  then  ortho, 
last  meta.  Lewis,  of  the  Sprague  Memorial  Institute,  experimenting 
on  animals,  found  meta  more  toxic  than  para. 

Paranitranilin  is  distinctly  important  in  dye  manufacture  not  only 
as  an  intermediate  for  sulphur  dj^es  and  for  azo  dyes,  but  also  because 
of  its  use,  together  with  beta-naphthol,  for  the  production  on  the 
fabric  of  a  bright  red  dye,  "  para  red."  The  most  conspicuous  action 
of  para  is  on  the  skin,  for  it  causes  a  very  distressing,  burning,  itch- 
ing eruption,  and  extraordinary  precautions  are  necessary  to  protect 
the  men  employed  in  grinding  and  packing  it.  It  is  also  capable  of 
producing  serious  and  even  fatal  sj^'stemic  poisoning.  Bachfeld*^ 
reported  nine  cases  of  poisoning,  four  of  which  Vv-ere  serious,  with 
frequent  scanty  micturition,  burning  pain,  but  no  blood  or  albumen  in 
the  urine.  A  fatal  case  was  reported  by  Lewin  from  the  Hochst 
factory.  The  man  had  been  working  for  five  hours  in  x^aranitranilin 
dust.  At  least  one  fatal  case  has  occurred  in  the  United  States.  A 
27-year-old  white  man  was  employed  for  12  days  in  the  paranitranilin 
department  of  a  color  works,  never  having  before  been  brought  in 
contact  with  anj^  of  these  compounds.  The  day  of  the  accident  he 
had  been  working  about  an  hour  in  the  drying  room  where  parani- 
tranilin is  dried  on  trays.  The  nature  of  the  accident  was  not  re- 
ported, but  he  was  said  to  have  been  poisoned  by  dust,  perhaps  from 
tipping  over  a  tray  of  the  powder.  He  was  sent  to  the  bathroom  and 
took  a  bath,  remaining  there  for  about  an  hour.  Then  he  went  to 
the   works   doctor,   and   after   he   had  been   in  the   office   about   20 

'''  Harnack.      Quoted   by   Kobert.      Lehrtach   tier    Intoxikationeu.      Stuttgart.      1011,    p. 
787. 

*"  Kobert.     Lebrbuch  der  Intoxikationen.     Stutt.gart,   1911. 

■"■' Rambonsek.  J.     Industrial  PoisonlDi>'.     Translated  bv  T.  M.  Les^e.     London.   1913. 
"s  Gibbs  and  Hare.     Quoted  by  Kobert.     Lehrbucli  der  Intoxikationeu.     Stutti>arl,  1911. 
■"  Bachfeld.     Vierteljahresebrift  fiir  gerlchtliche  Mediziu,  1898.     XV,  396. 


32  IXDUSTEIAL,   POISOXIXG   IX    MAKING    COM.-TAT.   DYES. 

minutes  he  lost  consciousness.  He  was  given  stimulants  and  the  lung 
motor  was  used,  but  he  died  two  and  a  half  hours  after  the  accident. 

IMetanitranilin  is  made  from  dinitrobenzene,  and  reports  of  indus- 
trial poisoning  from  this  department  are  sometimes  dubious,  be- 
cause it  is  impossible  to  be  sure  which  compound  is  the  cause.  Xever- 
theless,  clear  cases  of  meta,nitranilin  poisoning  do  occur  in  work  in 
which  no  DXB  is  present.  For  instance,  a  vcorkman  22  years  old 
was  told  to  clean  out  a  tub  in  which  metanitranilin  had  been  "  proc- 
essed.'" Soon  after,  he  complained  of  acute  frontal  headache,  then 
he  vomited  and  lost  consciousness.  He  was  taken  to  the  hospital  and 
the  record  reads :  Vomiting ;  fainting  attacks ;  headache ;  rapid  heart ; 
very  profound  cyanosis ;  lips  and  mucous  membranes  almost  black. 

A  similar  case  is  reported  by  the  Xew  York  Department  of  Labor 
from  another  American  plant.  Here,  too,  the  man  was  sent  to  clean 
out  a  munjer  in  which  metanitranilin  had  been  made.  He  worked 
off  and  on  from  9  in  the  evening  to  midnight.  At  midnight  he  went 
off  for  half  an  hour  for  supper  and  when  he  returned  he  told  the 
foreman  that  he  was  faint  and  nauseated,  but  nevertheless,  he  was 
alloAved  to  go  back  to  work.  At  half  past  4  in  the  morning  he  was 
found  unconscious  and  was  taken  to  the  hospital,  deeply  cyanosed, 
respiration  rapid  and  shallow,  pulse  rapid  and  of  poor  cjuality. 
Eight  ounces  of  venous  blood  were  removed,  the  color  was  dark  and 
it  coagulated  slowly.  He  was  given  saline  infusions,  but  he  did  not 
improve,  and  in  the  morning  transfusion  of  blood  (500  cc.)  was  made. 
Under  this  treatment  and  the  administration  of  oxygen  and  stimu- 
lants he  graduallv  improved^  but  did  not  regain  consciousness  till 
6.30  that  evening.    His  convalescence  was  very  slow. 

In  one  of  the  ordnance  plants  during  the  war  metanitranilin  was 
manufactured  on  a  large  scale  for  use  together  with  DXB  as  an 
explosive  in  high-explosive  shells.  There  was  much  ill  health 
among  the  men  working  in  this  department,  from  contact  and  from 
tlie  steam  in  the  course  of  washing.  The  men  in  charge  said  that 
the  poisoning  was  cumulative,  that  each  attack  lasted  longer  than 
the  previous  one.  The  symptoms  were  those  characteristic  of  an 
amido  compound,  with  verv  irritating  effect  on  the  skin. 

Methyl  and  ethyl  an?Im  {C .H.-N {CH,) ,,  CeH.XCC^H,)^).— The 
allrxd  derivatives  of  anilin,  dimethylanilin  and  diethylanilin,  are  dis- 
tinctly less  poisonous  than  anilin,  and  when  poisoning  does  occur  it  is 
possible  that  the  substance  responsible  is  really  unchanged  anilin.  One 
ease  that  was  reported  came  from  direct  contact.  A  stopcock  came 
off  and  a  mechanic,  in  trying  to  screw  it  on.  received  a  spurt  of 
dimethylanilin  in  his  face.  Another  case  was  caused  apparently  by 
dimethylanilin  fumes  in  the  earlier  days  of  American  dye  manu- 
facture, in  1916.*^  A  man  of  22  years  had  been  at  work  only  two 
weeks  on  the  night  shift.  At  half  past  10  he  climbed  a  ladder  to 
inspect  a  vat  of  dye  which  was  saicl  to  be  crude  violet  made  from 
carbolic  acid,  dimethylanilin,  and  other  substances.  He  lifted  the 
lid,  breathed  the  fumes,  and  lost  consciousness,  not  recovering  his 
senses  till  eight  hours  later.  The  cyanosis  in  this  case  was  so  deep 
that  the  doctor  summoned  to  the  plant  thought  he  must  have  fallen 
into  the  violet  dye.  The  next  day  he  was  taken  to  the  hospital  com- 
plaining of  impaired  vision,  noise  in  the  ears,  and  intense'  i^ain  in 
the  abdomen.     He  was  in  the  hospital  seven  days. 

— — — « ' 

^  From  the  records  of  the  New  York  State  Department  of  Lahor. 


ANILII^   AND   OTHER   AMIDO    COMPOUNDS.  33 

A  second  man  *^  treated  in  the  same  hospital  had  been  told  to  bail 
dimethylanilin  from  one  container  to  another,  in  the  course  of  which 
he  probably  got  some  of  the  liquid  on  his  hands.  He  worked  from 
8  in  the  morning  to  3  in  the  afternoon,  when  he  told  one  of  the 
chemists  that  he  felt  twitching  in  his  toes  and  feet,  gradually  spread- 
ing up  his  legs,  and  he  was  faint  and  nauseated.  The  chemist  made 
him  sit  down  in  the  open  air  for  an  hour,  but  he  did  not  wash  his 
hands  nor  change  his  clothes.  He  was  then  taken  home,  where  he 
grew  weaker  and  finally  lost  consciousness,  in  which  condition  he 
was  taken  to  the  hospital,  where  they  found  him  deeply  cyanosed 
and  with  a  weak  and  rapid  pulse.  Two  weeks  later  he  was  still 
weak  and  his  mind  somewhat  confused. 

Anilin  hydrochloride, — This  compound  of  anilin  produces  exactly 
the  same  symptoms  as  anilin  and  there  may  be  a  good  deal  of  poison- 
ing in  the  course  of  its  manufacture  unless,  as  is  usual,  the  work  is 
carried  on  in  an  open  shed  or  in  a  room  abundantly  supplied  with 
artificial  ventilation.  In  one  department  the  man  in  charge  said  that 
once  during  a  month  of  hot  weather  all  the  men  in  his  department 
were  cj^anosed.  He  said  that  the  worst  cases  came  from  letting  the 
hot  hydrochloride  splash  on  the  skin,  for  it  is  quickly  absorbed. 

The  fatal  case  of  anilin  poisoning  reported  hj  ^^-Tiite  and  Sellers 
at  the  Brussels  Congress  of  Industrial  Hygiene  in  1910  was  in  a 
man  working  with  anilin  hydrochloride,  but  it  was  caused  by  the 
anilin  itself,  which  splashed  over  the  man's  hands  and  face  and  body. 
He  died  within  24  hours'  time.  However,  it  must  be  remembered 
that  anilin  hj^drochloride  is  capable  of  producing  tjq^ical  anilin 
poisoning.  Price-Jones  and  Boycott  used  it  in  their  experiments 
instead  of  anilin  and  brought  about  ail  the  blood  changes  char- 
acteristic of  anilin. 

Less  important  is  svlfanilic  acid^  which  is  produced  in  the  same 
way,  only  by  the  use  of  sulphuric  instead  of  hj^drochloric  acid.  The 
same  risks  attend  its  production,  but  as  to  the  toxicity  of  the  finished 
product  there  seems  to  beno  information  in  the  literature. 

Benzaldelnjde  (CgH-CHO),  or  oil  of  bitter  almonds,  is  an  im- 
portant intermediate  which,  so  far  as  present  evidence  goes,  has  no 
toxic  effect.  Kobert*®  found  it  harmless  to  animals,  and  there  is 
,no  report  of  its  ever  having  caused  any  trouble  in  the  color  industry. 

P araamidovhenol  (CgH^OHNHj).- — Paraamidophenol,  which  re- 
sults from  the  reduction  of  paranitranilin,  is  an  important  inter- 
mediate, especially  for  sulphur  dj^es.  The  real  clanger  in  connection 
with  this  process  comes  from  the  paranitranilin,  which  is  distinctly 
the  more  poisonous  of  the  two.  Indeed,  the  excretion  of  both  nitro 
and  amido  compounds  from  the  body  is  preceded  by  their  reduction 
to  paraamidophenol,  which  is  found  in  the  urine  as  an  alkaline  s?Jt 
of  paraamidophenol-ether-sulphuric  acid. 

Paraamidophenol  is  one  of  the  substances  that  causes  troublesome 
dermatitis.  Nitro  so  dimethylanilin  (C6H4NON(CH3)o)  also  causes 
dermatitis.  The  naphthylamines  (CiqH-NHo),  alpha  and  heta^  are 
capable  of  producing  symptoms  characteristic  of  the  amido  com- 
pounds.   Alphanaphthyl amine  does  not,  so  far  as  appears  from  the 

^^  From  the  records  of  the  New  York  State  Department  of  Labor. 
^°  Kobert.     Lehrbuch  der  Intoxikationen.      Stuttgart,  1911. 

25431°— 21 3 


34  IXDUSTSIAL,   POISOXIIs-G   IIST    MAKIXG   CO.y:.-TAE   DYES. 

literature  and  from  the  testimony  of  practical  men,  set  up  a  serious 
form  of  poisoning,  but  one  of  the  earliest  cases  recorded  in  American 
literature  of  cj^anosis  from  an  amido  compound  was  Apf elbach's  *" 
second  case,  a  man  working  in  a  dry  color  factory  mixin.g  various 
compounds,  one  of  which  was  alphanaphthylamine.  Betanai^hthjd- 
amine  is  apparently  distinctly  more  toxic  than  filpha  and  in  one 
large  American  plant,  where  the  men  come  in  contact  with  it  in 
the  crude  naphthionic  department,  it  is  said  to  cause  not  only 
cyanosis  but  irequent  micturition,  perhaps  from,  over-acidity  of  the 
urine.  This  same  plant  has  no  trouble  at  all  with  the  alpha  com- 
}30und_.  A  ca.se  of  hematuria  from  ];etanaphthylan'iine  is  noted  in  the 
German  Factory  Inspection  Eeport  for  1912. 

There  are  a  few  more  compounds  containing  the  amido  group 
which  should  be  mentioned:  Anthranilic  acid^  used  for  lake  colors 
and  for  the  pigment  scarlet  B,  the  dye  used  for  postage  stamps,  is 
benzoic  acid  with  one  NHg  group  added  to  the  ring,  ortho-amido- 
benzoic  acid  (CgH^COOHXH^) .  It  is  only  slightly  poisonous  to  man, 
although  in  frogs  it  causes  paralysis.  Kleist  *'^  took  2  grams  within 
two  hours'  time  and  noted  discomfort  in  the  stomach,  salivation,  and 
sweating,  but  nothing  else.  The  methyl  ester  of  anthranilic  acid  is 
perfume  of  orange  blossoms.  None  of  the  derivatives  of  anthranilic 
acid  seem  toxic  to  warm-blooded  animals. 

Awddoazotoluene, — Amidoazotoluene,  called  scarlet  red,  is  known 
to  physicians  as  a  stimulant  for  tissue. growth,  and  therefore  useful 
in  severe  burns  to  hasten  healing.  As  a  rule  its  use  for  this  purpose 
has  not  been  followed  by  ajiy  untoward  symptoms,  but  two  cases  axe 
recorded  of  severe  poisoning  after  the  application  of  scarlet  red 
ointment  to  deep  burns.  Cyanosis,  dizziness,  headache,  pain,  slight 
rise  of  temperature,  rapid  pulse,  and  albuminuria  came  on  after  the 
application  of  scarlet  red.  The  symtoms  disappeared  when  the 
dressing  was  removed  and  recurred  when  a  second  application  was 
made.  Amidoazotoluene  is  derived  from  orthotoluidin  and  is  u.sed 
for  alizarin  color  manufacture. 

PhenyJJiydroxTjlamhie  is  said  to  be  formed  in  making  benzidin,  and 
when  this  occurs  a  bad  case  of  blistering  may  result  from  contact 
with  it- 

CHI.OE  COMPOUNDS. 

Chlorhenze-iie^  etc,  (Cf;IlgCl).=~The  chlorine  oompounds  of  the  ben- 
zene ring  are  considered  less  toxic  than  those  which  do  not  contain 
chlorine.  Experiments  made  by  Mayer  and  his  colleagues  for  the 
French  Government  -^  showed  that  chlorbenzene  is  less  toxic  than 
benzene  itself.  Nevertheless  it  is  possible  to  have  severe  poisoning 
from  chlorbenzene,  a.s  can  be  seen  in  the  cases  reported  by  Mohr.^^ 
Ten  instances  of  severe  and  typical  poisoning  are  described  by  Mohr 
in  men  who,  after  exposure  to  chlorbenzene  and  DXB  or  in  three 
instances  to  chlorbenzene  alone,  developed  the  symptoms  after  drink- 
ing a  few  glasses  of  beer. 

^1  ilohr,     Dent.-che  medizinisclie  Wochensclirift.     1902,  JXXVIII,  7:1. 
-srerkins.  R.  O.     United  States  Pahlic  H-ealth  Report-s,  ISl*).     Vol.  344,  p.  2;:'.35. 
-=  Apfelhacli,    G.   L.      Bullelin   of  Departmect  of  Factory   Jjispectlon  of   TlHnois,    1913, 
p.   5."). 

'"  Kobert.     Lehrbucli  dev  Intoxikationeo.     Stnttgart,  1911. 


CHLOE    COMPOUNDS.  35 

NitToclilor'hemene  (CgH^^ClNOa).  —  The  nitrochlorbenzenes  are 
very  rauch  more  poisonous  than  the  chlorbenzenes.  Systemic  symp- 
toms from  paranitrochlorbenzene  have  been  observed  in  connection 
with,  the  reduction  of  this  compound  to  paranitrochloranilin. 
Sturm  ^°  found  orthonitrochlorbenzene  very  volatile  and  the  fumes  de- 
cidedly toxic  to  animals  when  present  in  less  than  2-10  mg.  per 
liter  of  air.  It  is  more  toxic  than  para.  Para  is  an  intermediate 
for  sulphur  blue,  ortho  for  anisidin. 

Dinitrochlorbenzene  (CrH3Cl(NOo)2),  used  in  the  manufacture  of 
sulphur  blacks,  has  probably  caused  more  dermatitis  than  any  other 
compound  used  in  color  manufacture,  in  one  American  plant  every 
man  em])loyed  was  m.ore  or  less  affected  in  this  way,  and  for  a  while 
in  summer  the  place  had  to  close  down  for  lack  of  labor.  One  of 
the  men  described  the  symptoms  as  beginning  with  itching  behind 
the  knees  and  at  the  bend  of  the  elbow  and  along  the  inner  surface 
of  the  thighs.  Little  red  points  appeared,  which  later  coalesced  to 
form  a  swollen  mass,  which  itched  and  burned  unbearably.  Some- 
times the  face  was  involved  and  the  eyes  swollen  shut.  In  another 
plant  the  chemists  suffered  so  severely  from  dinitrochlorbenzene  itch 
that  they  were  forced  to  take  prolonged  alkaline  baths. 

Bemyl  chloride  (CgHgCHoCl)  is  toluene  with  1  atom  of  chlorine 
taking  the  place  of  an  atom  of  hydrogen  in  the  CH,  group,  and 
hemal  chloride  is  similar,  only  with  2  such  atoms  of  chlorine 
(C6H5CH(C1)2).  These  are  therefore  side  chain  products  and  not 
so  toxic  as  the  so-called  chlorinated  toluenes  in  which  the  hydrogen 
of  the  ring  is  replaced  by  chlorine  (CgH^CHgCl).  Benzyl  chloride, 
which  is  used  for  green  dyes,  is  one  of  the  many  "  tear  gases,"  pro- 
ducing rapid  and  intense  irritation  of  the  eyes  with  blinding  tears. 
Benzal  chloride,  which  is  used  to  produce  the  important  intermediate 
benzaldehyde,  is  still  more  irritating  to  the  ej^es.  In  the  only  place 
in  which  the  author  saw  benzjd  chloride  manufactured  chlorine  gas 
is  passed  into  toluene  and  the  resulting  benzyl  chloride,  carrying 
doubtless  chlorinated  toluenes  witli  it,  is  poured  out  and  washed  in 
an  open  shed ;  otherwise  the  fumes  would  be  unbearable. 

A  case  of  mixed  poisoning,  probably  from  chlorinated  toluenes, 
benzyl  chloride,  and  toluene  is  the  following:  A  chemist  was  em- 
ployed in  the  production  of  benzyl  chloride  and  was  working  in  an 
atmosphere  which  at  times  was  heavy  with  fumes.  During  the  nine 
months  he  worked  in  the  laboratory  he  lost  some  25  or  30  pounds, 
his  color  changed  to  a  cyanotic  hue,  he  suffered  from  insom.nia  and 
so  great  a  loss  of  strength  that  toward  the  end  he  found  himself 
unable  to  perform  the  sim]:)lest  sort  of  physical  work.  His  eyes  were 
affected,  but  transiently,  and  he  traced  it  to  the  benzyl  chloride,  for 
the  inflammation  varied  according  to  presence  of  benzyl  chloride 
fumes  in  the  air.  He  also  seemed  to  have  some  injury  to  the  liver, 
for  he  complained  of  pain  and  tenderness  in  the  liver  region.  No 
physical  examination  was  ever  made  in  this  case,  and  we  have  only 
the  history  to  go  by,  but  it  seems  pretty  clear  that  this  was  a  case  of 
XDoisoning  from  chlortoluenes  and  benzyl  chloride. 

5"  Sturm.  Quoted  bv  Curschmaun.  Deutsche  Vierteljalirsschrift  fih-  offentliclie  Gesund- 
heitspfiege,   1911.     XLIII,  22.5. 


36  INDUSTRIAL   POISOXIXG   IX    MAKIXG    COAL-TAE   DYES. 

HYDROXY   COMPOUNDS. 

Phenol,  hjTlrox}"  benzene,  lias  alreadj'  been  mentioned.  Na-phthol 
(CioH-HO),  which  bears  the  same  relation  to  naphthalene  as  phenol 
does  to  benzene,  resembles  phenol  in  its  action  but  is  less  soluble 
and  less  corrosive.  Alphanaphthol  is  more  strongly  antiseptic 
than  beta  and  probably  more  poisonous.  The  use  of  beta-naph- 
thol  in  industry  seems  to  give  rise  to  little  if  am^  trouble,  except 
for  its  effect  on  the  skin.  Even  the  fumes  are  said  to  be  irritating  to 
the  skin,  but  the  caustic  soda  used  in  the  production  of  beta-naphthol 
is  responsible  for  more  trouble  than  the  beta-naphthol  itself.  Xitroso- 
Ijeta-na/plitliol  formed  in  the  production  of  H  acid  gives  rise  to  derma- 
titis. 

Dinitronuphthol  (CioIIgO(X02)2)  is  the  dye  called  Martins  yellow 
and  also  Manchester  yellow.  It  has  the  usual  action  of  a  nitro  deriva- 
tive of  the  benzene  ring  on  the  blood  and  on  the  nervous  sj'stem,  but 
it  is  one  of  the  weaker  members  of  this  group. 

PYRIDINS. 

The  pyridins  used  in  the  making  of  anthraquinone  and  in  other 
processes  for  indanthrene  dyes  are  said  to  make  the  men  '"'■  dopy,"  to 
give  them  headache,  dizziness,  and  dulling  of  the  intelligence.  They 
have  also  a  peculiar  elfect  on  the  skin  similar  to  that  which  has  been 
described  in  England  as  a  result  of  the  handling  of  tarry  substances 
in  briquette  factories.  The  skin  is  raw  and  sensitive  as  if  from  sun- 
burn, and  the  man  suffers,  especially  after  washing  his  face  and 
hands  and  forearms  and  then  going  out  into  the  open  air. 

PHOSGENE  OR  CARBONYL  CHLORIDE   (COCl)e 

Phosgene  was  first  made  bj^  John  Dav^^  in  1812  by  exposing  a 
mixture  of  equal  parts  of  chlorine  and  carbon  monoxide  to  sunlight, 
and  he  gave  it  the  name  because  of  the  part  played  by  light  in  its 
formation.  It  was  used  for  some  years  before  the  war  in  dye 
manufacture,  especially  in  the  i^roduction  of  Michler's  ketone,  and 
it  was  resx^onsible  for  some  industrial  poisoning,  but  its  use  in  gas 
warfare  led  to  a  thorough  study  of  the  toxic  properties,  and' we  know 
now  ver}^  clearly  what  happens  when  phosgene  is  inhalecl.^^ 

It  owes  its  poisonous  action  to  the  fact  that  it  decomposes  readily 
in  the  presence  of  water  to  hydrocliloric  acid  and  carbon  dioxide. 
This  decomposition  takes  place  within  the  body  when  the  gas  reaches 
the  finer  bronchioles  and  the  alveoli  of  the  lungs  and  is  acted  on  by 
the  watery  vapor  there,  and  also  probably  when  the  gas  is  absorbed 
and  reaches  the  tissues  of  various  organs,  undergoing  slow  decom- 
position. The  effect  of  phosgene  differs  from  the  effect  of  hydro- 
chloric acid  because  it  is  not  immediately  caustic,  therefore  while  the 
latter  attacks  the  upper  respiratory  passages  and  produces  violent 
inflammation  of  the  larynx,  trachea,  and  bronchi,  phosgene  does 
not  produce  its  effect  till  it  has  penetrated  deeply  into  the  lungs. 

In  men  dying  from  phosgene  gas  the  lungs  are  found  deeply*  con- 
gested and  filled  with  fluid.     Around  the  fine  bronchioles  there  are 

=1  Collected  Studies  on  the  Pathology  of  War  Gas  Poisoning.  Medical  Science  Section 
of  the  Chemical  Warfai-e  Service.  M.  C.  Winternitz,  Major,  M.  C,  U.  S.  A.  Yale  Tniver- 
sity   Press,   1020. 


PHOSGENE    OR   CAKBOnSTYL    CHLORIDE.  3T 

islands  of  inflammation  which  form  broncho-pneumonic  areas  and 
may  spread  if  life  is  prolong-ed,  become  infected,  and  result  in 
miliary  abscesses.  The  edema  and  the  fibrin  which  obstruct  the 
circulation  in  the  lungs  lead  to  heart  strain  and  dilatation,  which 
may  be  the  immediate 'cause  of  death,  especially  if  the  victim  has  had 
to  exert  himself  after  gassing. 

The  German  factory  inspection  reports  for  the  year  1913  mention 
three  cases  of  poisoning  from  phosgene,  but  none  of  the  men  died. 
The  treatment  that  was  given  consisted  in  the  administration  of 
fumes  of  alcohol  mixed  with  oxygen.  So  far  no  fatal  cases  of  poison- 
ing from  this  substance  have  b,een  reported  from  English  dye  works, 
although  several  have  occurred  in  the  United  States.  It  is  impos- 
sible to  say  how  man}^  there  have  been  in  the  years  since  1914,  for  a 
great  deal  of  secrecy  has  been  observed  with  regard  to  them,  and  posi- 
tive statements  concerning  only  three  have  been  obtained.  One  of 
these,  which  should  really  be  attributed  to  the  gas  warfare  industry 
rather  than  to  the  dye  industry,  is  worthy  of  special  mention,  because 
it  shows  the  extent  of  the  danger  of  an  accident  which  allows  phos- 
gene gas  to  escape. 

In  a  plant  which  was  manufacturing  phosgene  for  use  in  the  war 
something  went  wrong  and  a  quantity  of  gas  escaped  at  a  moment 
when  about  180  men  were  in  the  vicinity  and  were  supposed  to 
have  breathed  more  or  less  of  the  fumes.  They  were  all  put  under 
medical  treatment  at  once,  and  20  developed  symptoms,  fairly  serious 
in  some  cases,  but  not  fatal.  An  Italian  teamster,  who  is  said  to 
have  been  more  than  1,000  yards  away,  was  not  thought  to  have 
been  exposed  and  was  allowed  to  go  on  with  his  work.  He  went 
hom.e  at  the  end  of  the  day  and  complained  of  breathlessness.  A 
doctor  who  was  summoned  said  he  was  develoiDing  pneumonia,  but 
by  5  in  the  morning  he  was  dead,  and  the  case  was  pronounced  to 
be  one  of  phosgene  poisoning.  One  of  the  ph3^sicians  in  charge  of 
the  other  men  said  that  they  suffered  from  intense  headache  which 
lasted  about  72  hours,  a  strangling,  exhausting  cough  without  sputum, 
exhaustion,  and  a  weak  heart.  One  man,  a  Negro,  developed  edema 
of  the  lungs  but  recovered. 

ALIPHATIC  OH  FATTY  COMFOUNDSo 

The  compounds  of  this  series  that  are  used  in  dye  manufacture 
are  methyl  and  ethyl  alcohol,  acetates,  chlorides,  aldehydes,  and 
ketones. 

According  to  Fraenkel,*'  the  members  of  the  methane  series  are 
less  toxic  than  those  of  the  ethylene  or  acetjdene  series.  The  toxicity 
increases  as  the  number  of  carbon  atoms  increase,  but  there  is  an 
important  exception  to  this  rule — methyl  alcohol  is  less  rapidly  toxic 
than  ethyl,  but  its  effects  are  more  serious  because  it  is  so  much  less 
rapidly  oxidized.  The  ethyl  series  have  a  special  affinity  for  the 
central  nervous  system,  and  most  of  the  ethyl  substitution  products 
are  more  poisonous  than  the  methyl.  Chlorine  increases  the  nar- 
cotic effect  of  all  fatty  compounds  and  also  the  depressant  effect  on 
heart  and  blood  vessels.  As  a  general  rule  the  toxicity  increases  with 
the  increase  of  CI  atoms,  carbon  tetrachloride  being  more  toxic  than 

"  Fraenkel,  Sigmuncl.  Die  Arzneimittel  Synthese  auf  Grundlage  der  Beziehung  zwischen 
chemischer  Aufbau  und  Wirkung,  Berlin,  1912. 


38  IXDUSTEIAL   POISOXI^s'G   IX    MAKING    COAL-TAB   DYES. 

chloroform.  Introduction  of  the  HO  group  lessens  toxicity  increas- 
ingly, changing  alcohols  to  giycolis  and  glycerines.  The  displace- 
ment of  an  HO  group  by  a  methyl  or  ethyl  group  increases  toxicity, 
especially  the  hypnotic  effect.  Esters,  ethyl  acetate,  and  amyl  ace- 
tate have  a  different  effect  from  alcohol,  increasing  respirations  and 
benumbing  the  central  nervous  system  without  any  exciting  effect. 

Methyl  or  to&od  alcohol  (CH.OH). — Industrialh^,  ethyl  alcohol 
can  be  disregarded.  One  hears  tales  of  workmen  having  been  made 
drunk  in  the  early  days  of  dye  manufacture  when  they  went  in  to 
clean  out  th«  stills,  but  the  work  of  still  cleaning  has  been  much  im- 
proved of  late  years;  air  is  blown  in  or  Draeg&r  helmets  provided. 
Methyl  alcohol  is  more  of  a  danger.  One  case  of  serious  systemic 
poisoning,  but  without  effect  on  the  e^^es.  occurred  as  the  result  of  a 
boil-over,  the  man  inhaling  the  fumes.  Two  cases  of  mixed  poison- 
ing are  on  record  in  the  files  of  the  Xew  York  Department  of  Labor. 
The  men  were  dipping  wood  alcohol  and  aniiin  from  rec-eptacles  and 
mixing  them. 

It  is  usually  assumed  that  the  use  of  denatured  alcohol  is  free  from 
danger,  but  this  is  far  from  being  true.  According  to  the  regula- 
tions of  the  United  States  Revenue  Service,  revenue-free  denatured 
grain  alcohol  can  be  produced  by  the  addition  of  methyl  alcohol  to 
grain  alcohol  in  quantities  from  2  to  20  per  cent.  There  is  also  a 
small  quantity,  about  one-half  of  1  per  cent  of  pyridin,  a  nauseous, 
ill-smelling  coal  tar  distillate.  The  denatured  alcohol  generally 
used  in  industry  contains  2  per  cent  or  4  per  cent  of  wood  alcohol, 
but  in  dye  manufacture  the  10  per  cent  formula  is  often  used  because 
the  Government  imposes  less  rigid  restrictions  on  the  use  of  this 
variety  of  denatured  alcohol.  In  one  color  works  it  was  this  10  per 
cent  methyl  alcohol  mixture  that  was  held  responsible  for  ill  health 
in  the  making  of  metanil  yellow  by  coupling  metanilic  acid  to  di- 
phenylamine  in  denatured  alcohol  containing  10  per  cent  of  methyl 
alcohol.  There  are  also  cases  of  susi^ectecl  methyl  alcohol  poisoning 
in  connection  with  the  making  of  methyl  aniiin  and  in  producing 
anisidin  from  nitroanisol. 

Experience  in  Germany  and  in  Austria  has  shown  that  denatured 
alcohol  which  contains  only  2  per  cent  methyl  alcohol  may  cause 
symptoms  of  poisoning  in  susceptible  workers.  The  variation  in 
individual  susceptibility  to  methyl  alcohol  is  very  striking,  as  was 
shown  in  the  famous  poisoning  in  the  Berlin  lodging  house  in  1911, 
when  more  than  a  hundred  men  were  made  sick  by  drinking  adul- 
terated brandy.  It  was  shown  then  that  the  same  amount  of  brandy 
which  had  produced  death  in  one  man  and  permanent  blindness  in 
another,  produced  only  trifling  symptoms  in  a  third.  Recently  a 
case  of  complete  blindness,  resulting  from  the  use  of  denatured  alco- 
hol with  4  per  cent  of  methyl  alcohol,  was  reported  by  J.  M.  Robin- 
son,^- of  Duluth. 

Of  the  aldehydes  of  this  series,  formaldehyde  is  the  important  one 
in  dj^e  manufacture.  It  is  used  in  the  production  of  synthetic  indigo. 
Iwanoff  '^^  tested  it  on  animals,  and  found  that  if  he  exposed  them  to 
heavy  fumes,  or  to  lighter  fumes  for  eight  or  nine  hours,  they  devel- 
oped purulent  bronchitis  and  edema  of  the  lungs.    Loeb  ^*  describes 

5- Robinson.     .Journal  of  American  Medical  Association,  1918.     LXX,  148. 

ss  Iwanoff.      Archiv  fiii-  Hy.criene,   1911.      IJi;XIII,  307. 

^*  Loeb.     Arch,   fiir   experimentelle   Pathologie  nnd   PJiarmakolog-ie,    1912.      XLIX,    114, 


ALIPHATIC    OR   FATTY   COMPOUNDS,  39 

also  affections  of  the  lungs,  but  in  addition  he  finds  that  all  the  alde- 
hydes of  the  fatty  series  cause  destructive  changes  in  the  coats  of  the 
arteries,  with  loss  of  elasticity  and  the  formation  of  aneurisms. 

The  ketones,  of  which  acetone  is  the  best  knoAvn,  seem  to  be  harm- 
less, at  least  no  harmful  effect  on  human  beings  has  so  far  been  re- 
ported. During  the  war  a  good  deal  of  acetone  was  used  in  making 
smokeless  powder,  but  no  harm  resulted.  Kobert  ^'^  believes  that  in- 
dustrial poisoning  from  acetone  is  impossible,  although  there  is  a  non- 
industrial  case  on  record  which  resulted  from  the  application  of  a 
celluloid  dressing  which  had  been  softened  by  acetone.  This  would 
tend  to  show  that  if  the  skin  is  in  contact  for  a  long  time  with  ace- 
tone, poisoning  may  occur.  Archangelsky  ^^  has  tested  acetone  on 
animals  and  has  found  that  it  is  possible  to  recover  it  from  the  brain 
a,nd  to  a  less  extent  from  blood  and  liver.  It  seems  to  have  a  special 
affinity  for  the  central  nervous  system.  It  is  narcotic,  but  only 
slightly  toxic.  Large  cjuantities  can  be  given  and  can  accumulate  in 
the  body  without  causing  death.  In  large  doses  a  narcosis  is  pro- 
duced like  that  of  alcoholic  intoxication,  from  which  recovery  is 
rapid  unless  excessive  quantities  have  been  given,  when  it  may  per- 
sist for  hours.  This  narcosis  can  also  be  produced  by  the  breathing 
of  acetone  fumes. 

Dimethyl  sulphate  ( (0113)2804)  is  used  in  dye  works  in  England, 
Germany,  and  the  United  States  to  methyiate  anilin.  It  is  not  essen- 
tial for  this  reaction  and  its  use  is  not  by  any  means  universal,  for  di- 
methylanilin  can  be  produced  by  the  use  of  methyl  chloride  or  methyl 
alcohol,  provided  the  reaction  is  carried  on  in  an  autoclave  with  hea-t 
and  pressure.  But  it  is  cheaper  to  use  dimethyl  sulphate  because 
heat  with  pressure  is  not  required.  The  poisonous  properties  of 
this  compound  are  well  known  and  in  many  of  the  plants  visited 
here  and  abroad  it  was  considered  too  dangerous  to  use,  but  in  others 
it  was  freely  used,  and  the  management  insisted  that  the  dangers 
had  been  greatly  exaggerated.  It  is  hard  to  believe  this  when  we 
are  told  that  it  was  one  of  the  gases  selected  by  the  Germans  for  use 
in  trench  warfare.^*' 

The  cases  of  industrial  poisoning  which  aroused  the  German  dye 
manufacturers  to  a  realization  of  the  danger  of  dimethyl  sulphate 
were  described  in  1902  by  Weber,^"  of  Schmiedeberg's  laboratory  in 
Strassburg.  There  were  three,  two  of  them  fatal,  and  they  had 
occurred  in  the  Bochringer  factory,  near  Mannheim,  and  in  the 
Ludwig  Casella  factory,  near  Hanau.  The  first  case  was  in  a 
laborer  48  j'-ears  old,  who  worked  for  four  hours  over  a  kettle  from 
which  heavy  gray  fumes'  of  dimethyl  sulphate  were  arising.  At 
the  end  of  this  time  he  felt  a  severe  burning  pain  in  his  throat  and 
chest.  He  went  to  the  doctor  and  48  hours  later  was  sent  to  the  hos- 
pital in  a  dying  condition  with  pneumonia  of  both  lower  lobes  and 
distinct  evidence  of  a  local  caustic  action  on  the  tliroat.  The  mucous 
membrane  of  the  pharynx  and  uvula  was  destro7y^ed  and  there  were 
also  burns  covered  with  scabs  on  the  eyelids.  He  died  that  same 
day.     The  autopsj^  showed  destruction  of  the  mucous  membrane  in 

^"Kobert.     Lehrbuch   dei-  Intoxikationen.      Stuttgart.    1911. 

^^  Archangelsky.  Archiv  fiir  experimeutelle  Pathologie  und  Pharmakologie.  1901. 
XLVI,   347. 

°o  Auer.  Proceedings  of  Societ.y  for  Experimental  Biology  and  Medicine,  1918.  Xv', 
104  and  106. 

^i"  Weber.     Arch,  fiir  experimentelh;  Pathologic  und  Pharmakologie,  1902.     XLVII,  113. 


40  IXDUSTEIAL   POISONING   IX    MAKING    COAL-TAR   DYES. 

larynx,  trachea,  and  bronchi,  small  hemorrhages  into  the  serous  cov- 
ering of  brain,  lungs,  and  heart,  cloudy  swelling  of  liver  and  kidneys, 
double  pneumonia. 

The  second  case  occurred  at  the  same  time  and  in  the  same  room. 
Another  laborer,  19  j^ears  old,  was  working  at  a  distance  from  the 
dimethyl  sulphate  kettle.  He  was  obliged  to  stop  work  because  of 
burning  in  the  chest,  constant  cough,  and  running  in  the  eyes.  For 
a  week  he  suffered  from  hoarseness  and  painful  cough,  pain  in  swal- 
lowing, difficulty  in  breathing,  burning  in  the  chest.  On  the  third 
day  the  cough  began  to  produce  a  very  abundant  purulent  bloody 
sputum  and  he  also  vomited  mucus.  He  had  a  slow  recovery,  the 
hoarseness  lasting  three  weeks,  abundant  sputum  four  weeks.  His 
lungs  were  not  normal  till  the  tenth  week,  and  the  inflammation  of 
the  eyes  persisted  for  three  months.    He  lost  12  pounds  in  weight. 

The  third  was  a  chemist  who  broke  a  receptacle  containing  di- 
methjd  sulphate  and  spilled  about  20  cc.  over  his  clothes.  This  hap- 
pened in  the  morning.  In  the  evening  he  began  to  have  severe  pains 
hi  his  body,  especially  the  legs,  pain  in  his  eyes  and  burning  in  the 
chest.  Early  the  next  morning  the  physician  who  was  summoned 
found  that  he  had  burns  of  the  first  to  the  third  degree  on  the  abdo- 
men, genitals,  and  thighs.  He  had  severe  inflammation  of  the  throat, 
bronchitis  with  an  incessant  painful  cough,  edematous  swelling  of 
the  eyelids,  and  his  eyes  could  not  stand  the  light.  There  was  no 
involvement  of  the  lung  tissue,  of  the  heart,  or  the  nervous  system. 
The  burns  improved,  but  the  secretion  from  the  bronchi  grew  more 
profuse.  Inflammation  of  the  lungs  set  in,  then  jaundice  and  albu- 
minuria, with  a  high  fever,  a  rapid  pulse,  and  death  on  the  fourth 
da}-.     There  was  no  autops}''. 

Dimethyl  sulphate  is  an  oily  colorless  fluid  which  boils  at  188°  C. 
{d70A^  F.),  but  vaporizes  at  room  temperature,  giving  off'  gray 
fumes  at  60°  C.  (122°  F.)  which  consist  of  dimethyl  sulphate  itself. 
Weber  found  that  its  toxicity  depends  on  the  whole  molecule,  not  on 
any  group  which  may  be  split  ofl\  such  as  methyl  alcohol  or  sulphuric 
acid.  The  striking  peculiarity  of  dimethyl  sulphate  is  the  intensely 
caustic  effect  on  all  tissues,  not  only  by  direct  contact  with  the  skin 
but  by  the  action  of  the  vapors  on  the  lung  tissue.  In  animals  it  pro- 
duces also  coma  and  convulsions.  There  is  no  j^ossibie  antidote  for  it; 
l^revention  is  the  only  cure. 

Eecently  experiments  have  been  carried  on  by  Auer,^°  of  the  Eocke- 
feller  Institute,  testing  the  effect  on  cats  of  exposure  to  the  fumes  of 
dimethyl  sulphate,  which  he  calls  a  war  gas.  Auer  reviews  a  Rus- 
sian article  by  Xaiding,  published  in  May,  1917,  in  which  the  anes- 
thetic effect  of  certain  war  gases  was  mentioned.  Naiding  found  that 
soldiers  gassed  with  chlorine  and  phosgene  had  lost  pain  sensation 
in  the  skin.  Auer  brought  about  a  very  marked  generalized  loss  of 
sensation  to  pain  in  cats  by  exposing  them  to  dunethyl  sulphate 
fumes,  and  this  was  so  pronounced  that  severe  operations  could  be 
performed  without  any  sign  of  pain.  If  the  animal  survived  the 
analgesia  was  sometimes  still  well  marked  six  months  afterward.  The 
effect  on  the  respiratory  tract  was  like  that  which  has  been  described 
in  man,  a  diphtheritic  inflammation  of  large  and  small  bronchi  and 
bronchials  followed  by  edema  of  the  lungs. 

■f^  Aner.  Proceedings  of  Society  for  Exj^erimental  Biology  and  Medicine,  1918.  XV,  104 
and  106, 


ALIPHATIC    OE   FATTY   COMPOUNDS.  41 

In  factories  in  y\^hich  dimethyl  sulphate  was  found  in  use,  the  only 
precautions  taken  are  against  a  caustic  action  on  the  skin.  The  men 
are  given  goggles  and  rubber  gloves,  but  in  one  plant  they  were  not 
using  even  those  and  were  handling  it  with  less  care  than  they  gave 
to  caustic  soda.  It  was  said  in  this  plant  that  only  one  really  bad 
case  of  blistering  had  occurred  and  that  burns  on  the  skin  or  in- 
flammation of  the  ejes  were  the  worst  accidents  that  could  be  ex- 
pected. 

The  surgeon  in  charge  of  the  National  Aniline  and  Chemical  Co., 
Buffalo,  Dr.  Ferdinand  D.  Mohlau,  has  recently  published^^  an  ac- 
count of  two  cases  of  dimethjd  sulphate  poisoning,  the  first  reported 
in  America.  Two  men,  aged  53  and  55  years,  were  exposed  on  May 
26,  1920,  to  contact  with  liquid  dimethyl  sulphate  and  to  the  fumes. 
They  did  not  notice  any  effect  at  first  beyond  a  slight  irritation  of 
the  throat  and  eyes,  but  during  the  evening  of  that  day  the  irritation 
of  the  eyes  and  throat  became  intensified,  and  infla^mmation  of  the 
bronchi  developed.  Cyanosis  appeared.  A  ph^^sician  v\^as  summoned 
to  see  one  of  the  men,  C,  that  night,  but  Dr.  Mohlau  did  not  see  the 
case  till  the  afternoon  of  the  following  day.  He  found  him  "delirious, 
vrith  a  severe  congestion  of  the  throat,  symptoms  of  bronchitis,  a 
severe  inflammatory  condition  of  the  eyes,  intense  pain,  photophobia, 
and  a  severe  migraine,"  The  second  man,  S.,  was  then  visited  and 
found  in  a  similar  condition,  but  later  on  his  symptoms  became  much 
aggravated,  acute  congestion  of  both  lungs,  edematous  condition  of 
throat  anci  larynx,  and  considerable  cyanosis,  S.  passed  into  a  coma- 
tose state,  and  during  recovery  from  his  pneumonia  he  relapsed  sev- 
eral times  Avitli  an  aggravation  of  all  symptoms.  C.  had  a  quick 
crisis  and  recovered  promptly,  but  at  the  time  of  writing,  some  six 
weeks  later,  both  men  were  still  suffering  from  photophobia  and  from 
the  damage  to  throat  and  larjmx,  S.  has  also  complete  loss  of  color 
vision  and  his  visual  field  is  reduced  to  one-tenth.  His  optic  nerve 
shows  pale  outer  edges  but  no  degenerative  changes  are  discernible. 

The  urine  examination  showed  in  both  cases  an  increase  in  the 
phosphates  and  sulphates,  v/ith  a  faint  trace  of  albumJn,  an  occasional 
hyaline  cast,  and  no  sugar. 

In  this  same  article  is  given  the  result  of  experiments  on  a  rabbit, 
carried  on  by  Charles  A.  Bentz  and  K.  L.  Cameron,  both  of  Bufi'alo. 
The  animal  was  exposed  to  the  fumes  of  dimethyl  sulphate  under  a 
bell  jar  and  died  promptly.  The  blood  was  dark  and  fluid  and  gave 
the  characteristic  bands  of  methernoglobin,  the  liver  and  kidneys  were 
congested  and  had  undergone  intense  degeneration,  and  the  lungs 
were  edematous. 

The  use  of  'methyl  chloride  or  chlormethyl  is  not  unattended  with 
danger,  as  the  Germans  have  found.  Kobert  says  it  is  one-fourth  as 
poisonous  as  chloroform.  It  is  very  volatile,  and  in  a  report  by 
Gerbis^^  histories  of  two  cases  are  given  of  poisoning  by  fumes  of 
methyl  chloride  in  machinists  who  had  to  clean  from  time  to  time  a 
gasometer  through  which  methyl  chloride  passed.  Both  were  elderly 
men,  which  may  explain  their  susceptibility.  They  had  attacks  of 
somnolence,  once  preceded  by  delirium,  and  both  had  marked  im- 
pairment of  sight. 

5^  Journal  of  Industrial  Hygiene,  November,   1920,  vol.  2,  No.  7,  p.   238. 
="  Gerbis.     Miinchener  medizinische  Wochensctirift,    1914.     LXI,   879. 


42  INDUSTRIAL   POISON'lJSrG  IX    MAKING    COAL-TAE   DYES. 

INORGANIC  COMPOUNDS, 

Tlie  heav}'  acids,  hydrochloric^  sulphuric^  and  nitric^  are  used 
ill  dye  manufacture  in  large  quantities,  and  the  fumes  from  these 
acids  or  from  their  anhydrides  form  one  of  the  most  difficult  prob- 
lems of  factory  management.  Hydrochloric  acid  and  chlorine  fumes 
are  encountered  especiallj^  in  the  making  of  anilin  hj-drochloride,  of 
benzidin  sulphate  from  benzidin  hydrochloride  and  the  making 
of  nigrosin  and  induiin,  Nitrous  fumes  are  given  off  in  all  nitration 
processes  and  must  always  be  removed  through  fume  pipes.  As  a 
usual  thing  such  pipes  are  not  provided  with  exhaust  suction  and 
are  efficient  only  when  ever^^'thing  works  well.  If  the  wind  is  in  the 
wrong  direction,  and  still  more  if  the  nitrator  is  overheated,  these 
fumes  may  escape.  There  are  records  of  serious  poisoning  from 
nitrous  fumes  in  making  dinitrotoluene,  mononitrobenzene,  parani- 
tranilin  and  nitroso-beta-naphthol.  The  fumes  of  sulphur  dioxide 
may  be  given  off  in  ail  sulphonation  processes,  and  during  the  early 
stages  especially  these  fumes  may  be  very  distressing. 

All  these  compounds  except  sulphur  trioxide  have  a  very  caustic 
irritating  action  on  the  respiratory  tract.  It  is  characteristic  of  them- 
that  the  effects  do  not  show  themselves  in  their  full  intensity  till 
some  hours  after,  usually  when  the  man  has  left  work  and  gone  home. 
There  is  always  more  or  less  strangling,  with  burning  of  the  throat, 
at  the  time  the  gas  is  being  breathed  in,  but  usually  these  sj^mptoms 
can  be  controlled  by  simple  treatment.  The  man  apparently  recovers 
and  then,  some  6  to  12  hours  later,  he  exhibits  the  symptoms  of 
acute  congestion  of  the  lungs. 

Sulphur  dioxide  may  be  formed,  but  rarely,  at  high  temperatures 
in  certain  reactions.  In  moist  air  or  in  contact  with  the  mucous 
membranes  of  the  throat  and  nose  it  takes  up  water  and  changes 
to  sulphurous  acid,  which  is  very  caustic.  Irritation  from  SOo  be- 
gins at  as  low  a  point  as  0.01  in  1,000  parts  of  air,  and  a  new  work- 
man may  be  made  ill  hy  0.03  part,  but  tolerance  is  quickly  estab- 
lished, and  men  can  work  in  an  atmosphere  much  more  highly 
contaminated  than  that.  Sulphur  trioxide  is  irrespirable.  It  is 
very  disagreeable  and  choking,  but  not  harmful,  for  it  can  not  com- 
bine with  water  and  is  breathed  out  again  unchanged. 

The  fumes  of  hydrochloric  acid  are  very  caustic  to  lips  and  tongue 
and  throat.  The  danger  limit  is  said  to  be  between  0.1  and  0.2 
part  per  1,000  parts  of  air.  Chlorine,  which  is  almost  two  and  a 
half  times  as  heavy  as  air,  is  asi^hj^-xiating,  paralyzing  to  the  cen- 
tral nervous  sj^stem,  and  irritating  to  the  respiratory  tract.  There 
is  an  abundant  literature  on  chlorine  poisoning  because  of  the  use 
of  this  gas  in  chemical  warfare.  Fortunately,  both  hydrochloric 
acid  and  chlorine  fumes  are  so  immediately  strangling  in  their 
effect  that  workmen  exposed  to  them  get  away  as  cjuickly  as  pos- 
sible and  so  escape  the  severer  effects. 

The  m.ost  serious  effects  result  from  nitrous  fumes.  Both  chlo- 
rine and  sulphur  dioxide  are  more  immediately  painful  and  chok- 
ing than  nitrogen  oxide  fumes,  and  therefore  a  man  makes  more 
effort  to  escape  from  them  and  seldom  is  so  severely  poisoned. 
Nitrous  fumes  can  be  breathed  more  freely,  and  in  many  industrial 


INORGANIC    COMPOUNDS.  43 

cases  these  poisonous  gases  reach  the  whole  of  the  lung  surface 
so  that  when  inflammation  develops  there  is  no  normal  tissue  left, 
and  death  is  inevitable. 

More  than  one  industrial  physician  employed  in  dye  works  lias 
said  that  he  dreaded  nitrous  fume  cases  more  than  any  other. 

According  to  Haldane,  exposure  to  0.5  part  per  1,000  parts  of  air 
for  hail  an  hour  is  enough  to  kill  mice,  death  coming  on  after  24 
hours. 

In  dye  manufacture  the  really  serious  cases  of  nitrous  fume  poison- 
ing result  usually  from  an  accidental  leak  of  fuming  nitric  acid,  or  a 
job  of  cleaning  or  repairing  in  an  acid  tank.  A  typical  case  of  the 
latter  was  related  recently.  The  man  went  into  a  tank  which  had 
contained  nitric  acid,  but  which  was  supposed  to  be  empty.  There 
was,  however,  a  small  amount  of  residu;e  at  the  bottom.  He  "  choked 
up  "  several  timxes,  and  when  his  work  was  finished  he  was  coug-hing 
and  had  a  burning  pain  in  his  chest.  On  his  way  home  he  stopped 
in  to  consult  his  doctor,  but  the  latter  found  no  signs  in  the  chest 
except  a  slight  bronchitis.  Early  in  the  morning  the  doctor  was  sum- 
moned to  see  him  and  found  him  dying  of  edema  of  the  lungs. 

The  cases  of  industrial  poisoning  from  nitrous  fumes  that  have 
been  reported  are  usually  severe  acute  poisoning,  and  if  the  man  re- 
covers it  is  assumed  that  his  recovery  was  complete.  The  physician 
does  not  follow  up  his  la,ter  history.  Therefore  we  have  little  in- 
formation about  the  permanent  damage  to  the  lung  tissue  which  may 
be  produced  by  such  an  accident,  even  when  the  man  has  apparently 
recovered  from  the  acute  symptoms.  There  is  one  report  from  an 
American  source  of  an  accident  involving  20  men  whose  subsequent 
history  was  followed  up  for  nine  months.  (Hall  and  Cooper .*'°) 
Four  01  them  died  of  pulmonary  inflammation,  but  only  two  from 
an  acute  attack  developing  immediately,  the  other  two  were  not 
affected  till  several  weeks  after  the  accident.  There  were  relapses 
in  one-third  of  the  survivors,  with  symptoms  like  the  original  attack. 
Eight  recovered  their  health  practically  entirely,  after  periods  run- 
ning from  90  to  210  days,  but  the  others  suffered  loss  of  weight, 
"nervousness,"  stomach  troubles,  cough,  pleuritic  pain,  difficulty  in 
breathing,  especially  if  the  air  was  smoky.  The  loss  of  weight  among 
these  men  was  from  20  to  40  pounds. 

Hydrogen  suljjJiide  or  sulphuretted  hydrogen.— In  the  making 
of  sulphur  dyes,  when  sulphur  and  sodium  sulphide  are  fused 
with  various  amido  compounds,  hydrogen  sulphide  may  be  evolved 
in  gaseous  form.  The  danger  of  this  is  greatest  in  connection 
with  the  sulphur  browns  and  khaki,  less  in  connection  with 
sulphur  black,  least  with  sulphur  blue.  It  is  poisonous  in  very 
small  quantities,  danger  to  life  beginning  at  0.75  per  1,000  parts  and 
1  to  1.5  per  1,000  is  rapidly  fatal.  It  is  very  much  dreaded  in  the 
dye  industry,  not  because  many  fatalities  have  resulted  from  it,  nor 
because  it  gives  rise  to  a  great  deal  of  ill  health,  but  because  of  its 
startlingiy  rai)icl  action.  It  seems  to  be  the  general  opinion  that 
sulphuretted  hydrogen  is  either  rapidly  fatal  or  does  little  damage. 
Men  who  are  "  knocked  out "  by  the  gas  either  die  without  recovering 
consciousness  or  they  come  to  after  an  hour  or  two  and  seem  none  the 

«"  Hall  and  Cooper.     Journal  of  American  Medical  Association,   1905.     XLV,  396. 


44  IXDUSTPJ.IL    POISOXIXG    IX    MAKIXG    COAL-TAE    UYES. 

^^■orse  for  it,  although  a  careful  phj^sician  does  not  allo\r  them  to  go 
back  to  work  for  a  clay  or  so.  Many  instances  have  been  given  of 
the  rapid  action  of  this  gas.  One  man  went  into  an  empty  pressure 
tank  in  a  sulphur  brown  department  too  soon  aft^r  it  was  emptied 
and  was  completely  knocked  out  in  five  minutes.  A  second  man  who 
bent  over  the  manhole  to  help  him  was  also  overcome,  but  neither 
died.  The  physician  who  told  of  this  thought  it  dangerous  to  let  a 
man  go  into  a  re<:ej)tacle  which  had  an  opening  no  larger  than  a 
manhole.  Several  cases  have  been  reported  of  pipe  fitters  or  car- 
penters who  were  working  on  a  platform  in  sulphur  dye  depart- 
ments being  overcome  by  the  fumes  so  that  they  fell  from  the  plat- 
form and  were  injured.  One  pipe  fitter  who  was  affected  by  these 
fumes  was  sick  for  four  days,  although  he  did  not  suffer  from  any 
accident.  Eumors  of  fatal  poisoning  have  been  heard,  but  have  not 
been  substantiated. 

llydrogen  arsenide  or  o.rsemuretted,  hydrogen. — There  is  a  very 
general  impression  in  the  minds  of  the  public  that  arsenic  is 
used  in  the  manufacture  of  anilin  dj^es  and  that  some  of  them 
are  poisonous  because  they  contain  arsenic.  This  belief,  which 
is  also  held  by  many  phj'-sicians,  is  founded  on  old  and  long  dis- 
carded methods  of  manufacture.  In  an  early  article,  written  by 
Sonnenkalb  in  1864,  there  is  a  description  of  the  original  methods 
used  to  produce  fuchsin  and  the  colors  derived  from  it.  As  at  pres- 
ent, anilin  was  made  hj  the  reduction  of  nitrobenzene  with  iron 
filings  and  acid;  only  acetic  acid  was  used,  instead  of  hydrochloric. 
Eosanilin,  which  is  colorless,  was  then  formed  by  oxidation  and  was 
the  starting  point  for  the  colors,  which  were  pvoduced  by  the  action 
of  organic  and  inorganic  acids.  The  oxidizing  substances  used  were 
the  oxide  and  nitrate  of  mercury,  red  lead,  arsenious  acid,  and  other 
less  poisonous  compounds.  Fuchsin  was  made  with  arsenious  acid 
(HgAsO^),  and  its  poisonous  qualities  were  dt.e  to  its  arsenic  content. 
This  method  is,  of  course,  no  longer  used. 

The  arsenical  poisoning  which  occurs  now  in  the  manufacture  of 
anilin  dyes  is  caused  by  the  accidental  evolution  of  hj^lrogen  arsenide 
(AsHg)  which  may  occur  in  connection  with  certain  processes,  espe- 
cially acid  reduction,  and  alkaline  reduction  when  followed  by  acidi- 
iicatioh.  These  processes  are  described  fully  in  a  later  section  (see 
p.  53).  It  is  a  subtle  and  powerful  poison,  causing  extensive  destruc- 
tion of  the  elements  of  the  blood  and,  as  a  consequence  of  this,  an 
acute  degeneration  of  liver  and  kidneys.  When  the  exposure  to  the 
fum.es  is  great  enough  to  set  up  acute  poisoning,  the  man  is  seized 
with  symptoms  which  maj^  suggest,  and,  in  fact,  probably  often  do 
suggest,  acute  anilin  poisoning.  He  is  nauseated,  complains  of 
cramps  in  the  stomach,  vomits,  complains  of  headache,  dizziness,  and 
faintness.  The  urine  is  dark,  another  resemblance  to  anilin  poison- 
ing. But  the  condition  lasts  longer  than  that  caused  by  anilin,  or 
even  by  dinitrobenzene.  The  case  does  not  clear  up,  but  grows  worse, 
the  urine  becomes  bloody,  anemia  is  profound,  jaundice  appears,  and 
signs  of  inflammation  of  the  liver.  The  man  may  pass  into  a  typhoid 
condition  lasting  for  days,  or  he  may  die  within  a  few  days,  deeply 
jamidiced,  withconstant  vomiting  of  greenish  fluid. with  strangury 
and  bloody  urine.  Autopsy  then  shows  hemorrhagic  inflammation 
of  liver  and  kidneys. 


INOEGANIC    COMPOUNDS.  45 

This  form  of  poisonino:  has  been  recognized  in  Germany  for  a 
good  many  years  and  carefully  guarded  against.  It  has  also  been 
studied  recently  by  physicians  of  the  British  Factory  Inspection  De- 
partment and  by  physicians  attached  to  the  British  works.  Accord- 
ing to  these  authorities,  it  is  only  prudent  to  take  into  consideration 
the  possibility  of  arsenical  poisoning  in  any  case  of  supposed  poison- 
ing by  a  nitro  or  amido  compound  when  the  symptoms  do  not  clear 
up,  but  profound  anemia  or  jaundice  appear.  In  such  cases  the 
urine  should  be  tested  for  arsenic.  A  record  of  16  such  tests  was 
shown  by  one  of  these  physicians.  In  almost  all,  traces  of  arsenic 
were  found  in  the  urine,  but  only  five  had  enough  to  be  of  signifi- 
cance. Four  of  these  five  men  were  working  in  the  benzidin  de- 
partm_ent,  where  most  of  the  accidents  from  hydrogen  arsenide  fumes 
have  taken  place.  The  fifth  was  also  engaged  in  a  reduction  process, 
producing  amidodiphenylamine  by  the  use  of  zinc  dust,  iron  filings, 
and  hydrochloric  acid.  No  symptoms  were  complained  of  by  two  of 
the  men,  but  their  color  was  livid  and  their  urine  dark.  The  symp- 
toms of  the  other  three  might  easily  have  passed  for  anilin  poison- 
ing, jaundiced  skin,  dark  colored  urine,  headache,  and  abdominal 
pains.  Obviously  it  is  very  important  to  distinguish  this  low-grade, 
chronic,  arsenical  poisoning  from  poisoning  by  a  nitro  or  amido 
compound.  It  is  distinctly  more  serious,  because  arsenic  is  a  cumu- 
lative poison  in  a  sense  in  which  no  organic  compound  can  be. 

To  illustrate  this  sort  of  accident  in  dye  manufacture,  three  Ameri- 
can cases  which  occurred  in  a  small  plant  in  New  Jersey  are  selected. 
This  factory  was  making  naphthionic  acid  from  alphanaphthyla- 
mine  and  sulphuric  acid,  and  also  benzidin  base  and  sulphate  by  a 
reduction  process  involving  contact  between  hydrochloric  acid  and 
zinc  dust.  The  construction  of  the  plant  was  crude,  and  fumes  from 
the  different  jDrocesses  were  allowed  to  escape  into  the  room.  One 
night  five  men  were  at  work  in  the  benzidin  department,  and  when  the 
acid  was  added  at  the  end  of  reduction  there  was  a  "  boil  over."  The 
fumes  affected  all  of  the  men  so  that  they  were  obliged  to  quit  work. 
Their  subsequent  history  was  obtained  partly  by  personal  interview 
with  one  of  them  and  partly  from  the  records  of  the  hospital  to  which 
two  were  sent. 

The  first  man,  C,  had  been  employed  in  the  plant  for  18  months, 
and  had  often  suffered  from  the  fumes  in  the  benzidin  department. 
On  this  night  he  went  home  feeling  very  ill,  so  that  he  could  not  even 
get  into  bed,  but  dropped  down  on  the  floor.  He  did  not  send  for 
a  doctor,  thinking  it  no  worse  than  former  attacks  until  he  saAV  that 
his  urine  was  the  color  of  blood,  when  he  became  alarmed,  for  this 
had  never  happened  before.  He  was  ill  for  about  three  months, 
suffering  from  pains  in  the  kidney  region,  a  band-like  feeling  around 
the  lower  part  of  his  abdomen,  intense  pain  in  the  back  of  his  head 
and  neck,  vomiting,  poor  appetite,  depression,  and  loss  of  strength. 
During  this  time  his  wife  said  that  he  looked  like  "  a  yellow  corpse." 
When  seen  about  18  months  later  he  still  had  pains  in  the  kidneys, 
headache  and  buzzing  in  the  head,  and  his  strength  had  not  returned. 

The  second  man,  E),  was  treated  at  home  for  about  two  weeks  for 
supposed  typhoid  fever,  and  no  details  as  to  this  part  of  his  history 
can  be  obtained,  but  probably,  judging  from  the  diagnosis,  he  had 
symptoms  of  abdominal  distress  of  an  aggravated  kind.     When  he 


46  II^s'DUSTRIAL,   POISOXIjSTG   IX    MAKIISTG   COAI.-TAE   DYES. 

was  finally  brought  to  the  hosf)ital  the  Wiclal  test  disposed  of  the 
typhoid-fever  theory.  He  was  then,  on  the  fifteenth  day  after  the 
accident,  in  a  semiconscious  condition;  there  were  ulcers  in  mouth, 
throat,  and  tongue ;  he  had  diarrhea  and  vomiting,  and  his  body  was 
shaken  with  tremors  of  the  muscles.  Albiunin  was  found  in  the 
urine,  but  no  blood.  There  was  a  very  marked  anemia,  the  red 
blood  corpuscles  being  reduced  to  1,780.000.  Both  spleen  and  liver 
were  enlarged.  In  spite  of  his  partial  delirium  he  showed  gTeat  pain 
and  difficulty  on  urination,  and  this  symptom;  increased,  together 
with  retention  of  urine,  diarrhea,  and  frequent  vomiting,  during  the 
two  days  in  the  hospital.  He  died  on  the  third  day,  but  no  autopsy 
was  made, 

E  went  to  the  hospital  48  hours  after  the  accident.  He  was  then 
jaundiced,  complaining  of  great  pain  in  the  lower  chest  and  over 
the  bladder,  vomiting  greenish  fluid,  voiding  blood-red  urine.  There 
was  also  pain  and  difficulty  in  urination.  These  symptoms  per- 
sisted for  two  days,  then  slowly  improved,  and  he  was  discharged  on 
the  sixth  day,  "  cured  "  according  to  the  hospital  record,  but  accord- 
ing to  C  he  has  never  recovered  his  health  since  then  nor  been  able 
to  do  a  full  clay's  work.  ISTo  blood  count  was  made  in  this  case,  but 
hemoglobin  was  found  in  the  urine. 

As  for  the  other  two,  one  never  reported  back  to  the  plant,  and  C 
knew  nothing  of  his  history.  The  fifth,  a  cousin  of  C,  recovered 
completel}^. 

There  seems  little  doubt  that  these  were  cases  of  poisoning  from 
the  escape  of  hydrogen  arsenide  when  acid  and  zinc  dust,  one  or  the 
other  containing  arsenic,  came  together  in  the  process  of  making 
benzidin.  That  the  diagnosis  of  anilin  poisoning  should  have  been 
made  is  natural,  for  anilin  also  is  a  blood  poison,  one  that  destroys 
the  red  corijuscles,  thus  causing  the  apj)earance  of  hemoglobin  in  the 
urine  and  later  possibly  jaundice.  Anilin  poisoning  is  also  accom- 
panied by  more  or  less  pain  in  the  abdomen  and  by  vomiting,  but  all 
these  symptoms  were  more  accentuated  and  persistent  in  the  cases  in 
question  than  they  are  in  anilin  poisoning.  Xo  case  of  the  latter  is 
on  record  in  which  the  victim  passed  into  a  typhoid  condition  lasting 
for  days  and  terminating  in  death.  On  the  other  hand,  the  histories 
of  ail  these  cases  are  very  typical  of  arseniuretted  hydrogen  poisoning. 

Ccvustws. — The  caustics  used  in  dye  manufacture  are  sodium  hy- 
drate^ or  caustic  soda.  XaHO,  which  is  used  in  so-called  hydrolyzing 
or  caustic  fusion  (see  p.  51)  ;  soda-mid.^  NaXH,,  used  to  change  phenyl- 
glycine  to  indoxyi,  in  the  course  of  which  reaction  fumes  of  ammonia 
may  be  given  off;  and  m/)7iOGKlGracetic  acid,  which  is  used  in  the 
manufacture  of  indigo. 

It  is  not  necessary  to  describe  the  effect  of  caustic  soda  upon  the 
skin  and  mucous  membranes  of  nose  and  throat  and  on  the  conjunc- 
tiva, for  this  effect  is  famnliar  to  every  one.  Sodamid  is  not  so  pow- 
erful a  caustic.  In  contact  with  a  sweating  skin  it  changes  to  NaHO, 
and  therefore  it  acts  more  slowly  than  caustic  soda.  Monochloracetic 
acid  causes  severe  blistering  and  extensive  desquam^ation,  the  skin 
combing  ojff  in  sheets,  but  if  the  burn  is  treated  promptly  and  not 
allowed  to  become  infected,  there  is  almost  no  pain  connected  with  it. 

Fumes  of  aminon'm  have  given  rise  to  two  cases  of  serious  inflam- 
mation of  the  lungs,  with  edema,  in  the  dye  industry,  in  connection 
with  the  manufacture  of  indigo  and  of  aurantia. 


SICKNESS   IK   GEEMAN   DYE    MAKUFACTUEE.  47 

RECORDS  OF  SICKNESS  IN  GERMAN  DYE  MANUFACTURE, 

A  careful  search  through  German  factory  inspection  reports  for 
the  seven  years  just  i^rcceding  the  war  shows  the  following  substances 
to  be  responsible  for  occupational  poisoning  in  the  color  industry' : 

Anilin.  Hydrogen  sulphide. 

Nitrobenzene.  Chlorine  gas. 

Paranitranilin,  Phosgene. 

Toiiiidins,  ortho,  and  para.  Nitrous  fumes. 

Paranitrotoluene.  Pyrogallic  acid. 

Alpha  and  beta  naphthylamine.  Potassium  bichromate. 

Dinitrobenzeue.  Monochloriodide. 

Hydroquinone  and  other  (luinones.   Phosphorus  pentachloride,  and  oxj'cliloride. 

Chloranthracene.  Methyl  chloride  or  chloromethyl. 

Dimethylsulphate. 

Several  detailed  studies  have  been  made  of  sickness  in  certain 
German  plants.  For  instance,  such  a  report  is  given  of  a  factory 
employing  251  meii,  in  which  there  were  during  a  year's  time  33 
cases  of  industrial  poisoning,  with  500  days  of  sickness.  For 
the  workmen  not  emploj^ed  in  the  anilin  department  the  average 
was  0.97  attack  of  illness  per  man,  each  attack  averaging  14.G  clays. 
For  the  anilin  department  the  average  was  1.74  attacks  of  illness, 
with  23.48  days.  Ten  per  cent  of  the  cases  in  the  nonanilin  depart- 
ments were  skin  diseases;  41.8  per  cent  of  those  in  the  anilin  depart- 
ment were  skin  diseases.  Digestive  troubles  made  up  17.4  per  cent 
of  the  nonanilin  workers;  45.4  per  cent  of  the  anilin  workers.  Some 
unusual  cases  are  described.  One  was  a  boiler  tender  who  was  using 
water  from  an  anilin  still.  Some  of  it  boiled  over  and  soaked  the 
floor  and  the  coal,  and  he  had  a  severe  attack  of  anilin  |)oisoning.  A 
case  of  bloody  urine  occurred  in  a  man  making  naphthol,  and  an- 
other in  a  man  making  "  fuchsin  melt,"  There  was  one  death  from 
benzene  poisoning.  A  workman  vvent  into  a  room  which  he  had  been 
vfarned  not  to  enter  because  benzene  had  run  out  on  the  floor. 

Grandhomme,®^  who  M^as  for  many  years  physician  to  one  of  the 
great  German  dye  works,  analyzed  1,163  cases  of  sickness  in  the 
force  in  five  years,  1874  to  1879.  In  the  manufacture  of  anilin  colors 
there  was  an  average  of  60  per  cent  of  sickness,  in  making  alizarin 
colors  46  per  cent,  and  in  the  mechanical  department  40  per  cent. 
But  the  a'\^erage  length  of  disability  was  greater  among  the  men  in 
the  alizarin  department  than  in  the  anilin  because  there  was  a 
greater  proportion  of  skin  aitections,  and  these  are  notoriously  slow 
to  heal.  There  is  far  less  sickness  shown  in  the  more  recent  reports, 
as  indicated  in  the  next  paragraph. 

In  the  report  for  the  year  1913  a  factory  with  9,376  men  had  12 
cases  of  aniiinism,  with  98  days  of  sickness.  The  two  serious  cases 
in  this  factory  were  caused,  one  by  the  spilling  of  anilin,  the  other 
by  repair  work  in  an  imperfectly  cleaned  apparatus.  The  first  man 
got  his  clothes  soaked  with  anilin,  was  m.ade  to  strip  at  once  and 
take  a  thorough  bath,  but  in  spite  of  that  half  an  hour  later  he  became 
cyanosed.  The  second  man  was  a  lead  burner  working  in  a  receptacle 
which  had  contained  nitrobenzene  and  had  not  been  thoroughly 
cleaned.     He  was  ill  with  nitrobenzene  poisoning  for  eight  days. 

^  Grandhomme.     Vierceljahrssclirift  ifiir  gerichtliche  Medizin,    1S80.      XXXII,   120  and 


48  INDUSTRIAL,   P0IS02n^ING   12>r    MAKIISTG   COAL-TAE   DYES. 

RECORDS  OF  SICKNESS  IN  AMERICAN  DYE  WORKS. 

Cases  of  iDoisoning  have  occurred  in  the  United  States  from  the 
followino-  substances  used  in  the  making  of  d3^es  and  dye  inter- 
mediates : 

Benzene.  Paraamidopheuol. 

Toluene.  Dinitrophenol  1-2-4. 

Mononiti'Obenzene.  Paraphenyleudiamine. 

Dinitrobenzene.  Metapheuylendiamiue. 

Paranitrochlorbenzene.  ]S"itrosobetanaphtliol. 

Orthonitrochlorbenzene.  Alphanaphtbylamine. 

Dinitrodilorbenzene.  Betanaphthylamine. 

Anilin.  Benzanthrene. 

Paranitranilin.  Anisols. 

Metanitranilin.  Quinones. 

Dimetiiylanilin.  Phenyl  cavbyla  mine. 

Diethylauilin.  Phenylbydroxylamine. 

Anilin   liydrocbloride.  Solvent  naphtha. 

Paranitrochloranilin.  Pyridin. 

Nitroso  dimethjdanilin.  Kitric  acid  and  nitrous  oxides. 

Paranitrotoluene.  Sulphuric  acid  and  sulphur  dioxide. 

Dinitrotolnene,  Hydrochloric  acid  and  chlorine. 

Orthotoluidin.  Hydrogen  sulphide. 

Paratoluidin.  Hydrogen  arsenide. 

Paranitrotoluidin.  Monochloracetic  acid. 

Orthonitrotoluidin.  Sodamid. 

Acetylparatoluidin.  Sodium  hydroxide. 

Benzylchloride.  Ammonia. 

Chlorinated  toluene.  Methyl  alcohol. 

Paranitrophenoi.  Phosgene. 

Cyanosis  from  the  handling  of  nigrosin  has  been  reported,  but 
probably  should  be  attributed  to  anilin.  Cases  of  dermatitis  are 
said  to  occur  among  men  making  azo  colors,  and  the  condition  is 
called  "  azo  itch."  It  is  doubtful  whether  the  cause  is  to  be  found  in 
the  finished  colors.  It  would  seem  more  probable  that  it  should  be 
attributed  to  one  of  the  nitroso  intermediates. 

In  treating  climethylanilin  with  sodium  nitrite  the  nitroso  com- 
pounds of  the  corresponding  bases  are  formed  and  these  are  laiown 
to  be  very  irritating.  It  is  possible  that  in  making  azo  dyes  some 
nitroso  might  be  formed,  as,  for  instance,  when  the  amine  to  be 
treated  with  the  nitrite  is  impure  and  contains  phenols  or  secondary 
or  tertiary  amines. 

In  an  industry  so  new  as  the  anilin  color  industry,  it  is  very  im- 
portant to  know  not  only  which  are  the  possible  dangers  which 
threaten  the  workmen,  but  which  are  really  serious  and  which  are 
only  exceptionally  serious.  We  have  records  from  three  large  Ameri- 
can factories  which  throw  some  light  on  this  question.  In  one  of 
these  the  different  processes  have  been  classified  according  to  their 
danger,  so  that  the  examining  physician  may  decide,  on  the  basis  of 
the  phj^sical  condition  of  the  applicant  for  work,  in  which  depart- 
ment he  can  be  safely  placed.  There  are  three  classes  of  processes. 
Class  1  includes  operations  or  processes  in  which  nitro  or  amido 
compounds  are  used  and  which  experience  has  shown  involve  risk 
of  poisoning  to  the  workman.  Under  this  classification  come  the 
following  departments :  Naphthionic  crudes,  dinitrobenzene,  the  dia- 
mines, the  so-called  "  anilin  dyes  " — rosanilin,  magenta,  luchsin,  anilin 


SICKNESS    IN   AMEEICAN    DYE   WORKS.  49 

blue,  alkali  blue — plienjdgiycin  drying,  anthraquinone,  pyridin,  in- 
dantlirene  yellow. 

Class  2  includes  operations  or  processes  involving  the  handling 
of  nitro  or  amido  compounds,  but  which  are  attended  with  less  risk, 
either  because  the  poisoning  set  up  is  less  severe,  or  because  the  equip- 
ment is  so  arranged  that  there  is  no  contact  with  the  poisonous  sub- 
stances. In  this  class  come  paranitranilin  purification,  betanaph- 
thjdamine,  anilin  reduction,  benzidin  manufacture,  auramine,  and 
benzanthrene. 

Class  3  includes  operations  which  do  not  involve  handling  nitro  or 
amido  compounds,  or  in  which  such  compounds  are  present  but  no 
ill  effects  have  thus  far  resulted  from  such  work.  This  class  is.  large 
and  includes  the  ortho  and  paratoluidin  department,  sulphonating 
processes  of  all  kinds,  all  low-pressure  autoclave  work,  naphthionic 
purification,  picramic  acid,  benzoic  acid,  chloracetic  acid,  salicylic 
acid,  chlorine,  hydrochloric  acid,  chlorbenzene,  benzaldehyde,  sodium 
sulphide,  nitranisol,  eosin,  victory  green,  malachite  green  and  sulphur 
black  and  indigo. 

The  record  of  a  plant  in  which  about  850  process  men  are  em- 
ployed and  about  400  laboratory  men  is  as  follows  for  one  month  of 
hot  summer : 

Cases. 

Poisoning  from  nitro  and  amido  compounds,  new  cases 29 

Poisoning   from  nitro  and   amido    compounds,    old   cases   still 

under  treatment 26 

Acid  burns  of  cornea 20 

Acid  burns  of  cornea,  with  conjunctivitis 29 

Dermatitis 122 

Alkali  in   eye,   inflammation 26 

Alkali   burns 82 

Chlorine  fumes 1 

The  improvement  that  has  taken  place  in  this  plant  within  the 
last  year  is  shov\^n  by  the  record  of  days  lost  on  account  of  occupa- 
tional disease  in  relation  to  the  output  of  the  plant.  There  was  at 
first  a  great  deal  of  trouble  in  the  ortho  and  paratoluidin  area,  and 
for  a  time  the  cases  of  poisoning  were  very  frequent.  Then  exhaust 
ventilation  was  installed  to  remove  fumes  not  only  from  the  liquids 
but  from  the  solids  also.  The  men  were  given  rubber  boots  and 
gloves  and  they  were  strictly  watched  and  sent  to  the  hospital  for 
treatment  at  once  if  the  slightest  sign  of  illness  appeared.  The  days 
lost  on  account  of  poisoning,  which  in  December  had  been  61  for  an 
output  of  125,000  pounds,  had  reached  zero  in  June  with  an  output 
of  340,000  pounds. 

For  a  second  plant  the  records  for  six  months  in  1918,  from  Janu- 
ary to  July,  are  available. 

The  number  employed  at  this  time  was  about  1,600,  something  over 
700  of  whom  were  process  men  and  about  100  engaged  in  laboratory 
work.  The  company  considered  only  cases  of  acute  fume  poisoning 
or  of  injury  to  skin  or  eyes  by  acids  and  caustics  as  "occupational" 
in  character,  so  in  order  to  get  at  the  amount  of  illness  in  the  dif- 
ferent departments  one  must  look  through  the  list  entitled  "non- 
25431  °—2i 4 


>0 


IXDTJSTKIAL   POISOXIlsrG   IX   MAIQITG    COAL-TAE   DYES. 


occupational. "    This  gives  the  number  of  cases  among  1,640  men  in 
six  months  as  follows : 

Cases. 

Gasu'o-iQtestiiial  diseases @3 

Colds,  catarrii,  coughs,  grippe 60 

Lumbago,  riieumatistn,  etc 12 

Headaclie 13 

Abscesses,  boils,  etc 2T 

Skin  eriiptioiis 37 

Conjunctivitis  and  sundry  eye  diseases 72 

Unclassified -13 

Total 338 

The  different  classes  of  employees  snifered  in  the  folloTving  pro- 
portions diirina^  the  six  months : 


eiass. 

NujTL>.c-r  of 
omployees. 

Grses  of 
'  sieliaicsr.. 

Per  cent 
siek. 

627 
200 
97 
300 
270 
146 

116 
11 

IS 
S5- 
73 
33 

IS.  5 

5.5 

IS.  6 

2S.3 

27  0 

Raw  materi'^ls 

22.6 

During  the  same  period'  a  record  of  accidents  was  kept^  both  those 
involving  loss  of  working  time  and  those  needing  treatment  but  with- 
out loss  of  time — minor  accidents. 


Character  of  injury. 


Add  bunas 

Caustic  soda  burns 

Steara  and  litiuid  burns 

Bui'us  from  explosions 

Sundry  burns  ~ 

Aicilta  poisoniTLg 

ISfitrous  ii.unes 

Simdry  fumes 

Injuries  to  sye  (not  mechanical): 

From  acids -".... 

From,  caustics  and  lime 


Total. 


AceidenJ'S 

causLn'?  loss 

of  time. 


Days  lost. 


1,605 
13 
15 
21 

74 


Minor 
accidents. 


It  is  impossible  to  read  these  figures  and  not  see  the  influence  of 
the  occupation  on  even  the  supposedly  nonoccupational  diseases 
given  in  the  second  table.  The  worlonen  who  come  in  contact  with  the 
raw  material,  intermediates,  and  colors,  have  a  decidedly  higher 
sickness  rate  than  have  the  workm.en  p,ot  so  exposed. 

PROCESSES  m  BYE  MANXJFACTURE, 

It  is  not  the  purpose  of  this  report  to  describe  the  very  compli- 
cated processes  of  dye  manufacture  except  so  far  as  it  m.ust  be  done 
in  order  to  point  out  the  possible  dangers  to  the  workm-en.  Only  a 
bare  outline  is  presented  of  the  principal  reactions,  in  connection 
with  the  consideration  of  the  special  risks  involved  in  each.  It  is 
impossible  to  generalize  about  the  dangers  of  the  color  industry,  the 
various  departments  of  which  differ  so  much  in  character. 


PROCESSES    il>r    DYE    MANUi'/iCTUl-lE.  5-1 

There  are  certain  fiindamentai  chemical  processes  that  are  iised 
ill  dye  production  and  that  cany  with  them  clangers  which  are  some- 
times constant,  inherent,  and  ¥/ell  recognized :  others  that  are  acci- 
dental and  perhaps  quite  unforeseen  hj  all  but  very  experienced  men. 
These  processes  are  as  follows:. 

1.  SuVphonntlon^  or  treatment  with  faniing  sulphuric  acid,  usually 
added  in  excess.  This  very  common  procedure  results  in  the  re- 
placement of  an  TI  atom  in  an  organic  compound  by  the  sulphonic 
acid  (SOgHO)  group,  and  often  the  change  from  a  toxic  to  a  non- 
toxic or  weakly  toxic  body.  The  troublesome  features  of  sulphona- 
tion  lie  in  the  nature  of  the  body  to  be  sulplionated,  anilin,  toluidins,- 
etc.,  and  in  the  fumes  of  SOo  that  m.ay  be  given  off  if  a  good  fum.e 
pipe  S7/steni  has  not  been  iristalied  or  if  sulphonating  tubs  are  left 
partially  uncovered.  These  fumes  may  be  very  disagreeable,  espe- 
cially during  the  early  stages  of  the  reaction.  In  one  plant  the  fore- 
man remarked  that  v/hen  the  sulphonators  were  charged  they  ex- 
pected "  a  gas  attack  lasting  about  five  minutes,  during  which  time 
everyone  takes  to  cover."  SO3  is  not  dangerous,  but  at  a  high,  tem- 
perature it  may,  through  the  oxidation  of  organic  matter,  change  to 
SO2,  as  when  anilin  sulphate  is  heated.  Then  sulphonation  and 
partial  oxidation  result  in  the  formation  of  sulfanilic  acid  and  SOo. 

2,  Caustic  fusion.,  or  ca-ustic  meltmg  or  Jiydrolyzvng. — It  is  usu- 
ally a  sulphonated  product  that  is  fused  with  sodium  hydroxide, 
and  the  SOgOB,  group  is  replaced  by  a  h7/d.roxyI  (OH)  group.  In 
this  way  benzene  monosulphonic  acid  yields  hydroxy-benzene  or 
phenol,  and  naphthalene  monosulphonic  acid  yields  alpha  and  beta 
naphthol.  The  danger  here  is  from  the  sodium  hydroxide,  not  only 
from  contact  v/ith  the  solid  or  liquid  fornr  but  even  from  exposure 
to  steam  which  carries  it.  Caustic  bum.s,  sometimes  very  severe,  are 
fairly  common  in  connection  with  this  process,  and  even  in  the  best- 
managed  factories  the  danger  has  not  been  entirely  done  away  with. 
If  the  sodium  hydrate  is  added  to  a  liquid  in  the  kettle  there  is  great 
danger  of  splashing;  it  should  always  be  put  in  first.  Methods  of 
handling  the  caustic  differ  much  in  difrerent  plants;  sometim.es  it  is 
handled  in  solid  form,  shoveled  or  scooped,  but  this  gives  trouble 
with  dust,  especially  in  hot  weather  when  it  dissolves  on  the  sweat- 
ing bodies  and  causes  a  great  deal  of  irritation.  Or  the  container 
is  heated  and  the  liquid  contents  are  blown-  to  the  hydrolyzer.  This 
is  much  safer  if  all  goes  well,  but  productive  of  more  serious  acci- 
dents if  anything  goes  v^^rong  and  the  liquid  caustic  splashes  about. 
Another  disastrous  accident  is  the  blowing  up  of  an  autoclave  used 
for  caustic  fusion,  scattering  the  hot  caustic  and  causing  terrible 
burns  of  skin  and  eyes. 

In  the  making  of  betanaphthol,  which  is  alwaj^s  disagreeable 
work,  hot,  sloppy,  steaming-,  ill  smelling,  it  is  chiefly  the  use  of 
caustic  soda  that  gives  trouble.  Naphthalene  is  sulphonated,  the 
resulting  alpha  and  beta  salts  are  separated  by  liming  (treatment  with 
Cfilcium  to  form  the  soluble  alpha  and  insoluble  beta  salt),  the 
calcium  is  replaced  by  sodium,  and  the  sodium  salt  of  betanaph- 
thalene  sulphonic  acid  is  fused  with  caustic  soda.  It  is  here  that 
the  escaping  steam  may  carry  caustic  with  it.*^- 

^  Tbe  most  recent  process  if  or  making  betanaphthol  is  without  liming.  Nnphtha.ene  is 
sulphonated,  the  sulphonation  mixture  is  neutralized  with  soda  R.«-h  and  salted  out,  the 
beta  salt  is  filtered  out  and  fused  to  hetanaphthol. 


52  INDUSTRIAL   POISONI]S"G   IX    MAKIjSTG   COAL-TAR   DYES. 

In  boiling  p-nitracetanilid  with  sodium  hydrate,  if  the  boiling  is 
carried  too  far  decomposition  may  take  place  and  anilin  and  am- 
monia be  given  off.  There  is  always  an  effort  made  to  provide  for 
the  possible  escape  of  fumes  here, 

3.  Nitration. — A  mixture  of  nitric  and  sulphuric  acids  is  used 
for  nitration,  the  latter  being  added  to  take  up  the  water  liberated 
in  the  reaction,  which  would  otherwise  result  in  too  great  a  dilu- 
tion of  the  nitric  acid.  The  most  usual  nitration  process  in  dya 
manufacture  results  in  the  production  of  a  mononitro  compound, 
a  single  NO,  group  replacing  one  hydrogen  atom  in  the  benzene 
ring.  For  dinitro  and  trinitro  compounds  further  nitration'  is 
carried  on  in  successive  steps  usually.  The  danger  in  tiiis  process 
is  that  which  always  attends  the  use  of  nitric  acid.  Not  only  may 
severe  burns  result  from  splashed  acid,  but  the  fumes  of  mixed 
nitrogen  oxides  that  are  given  off  when  nitric  acid  is  exposed  to 
the  air  or  when  it  is  added  to  the  organic  substances  to  be  nitrated 
constitute  one  of  the  gravest  risks  to  which  the  workman  in  the  dye 
industry  is  exposed. 

It  must  also  be  remembered  that  the  product  resulting  from  ni- 
tration is  more  toxic  than  the  original  compound  and  requires 
great  care  in  handling.  Eeference  has  already  been  made  to  the 
difficulty  encountered  with  tlie  making  and  use  of  dinitrobenzene, 
nitranilins,  dinitrophenol,  to  mention  only  the  worst  of  these  com- 
pounds. The  waste  acid  from  the  nitrators  is  also  a  source  of  danger, 
for  it  oft-en  carries  enough  of  the  product  of  nitration  to  cause 
j)oisoning.  In  making  DNB,  the  first  waste  acid  may  contain  as 
much  as  20  per  cent  DNB,  and  must  be  used  again  and  again  to 
recover  it.  The  manufacture  of  DNB  from  mononitrobenzene  is 
almost  always  the  most  troublesome  department  of  all,  and  in  some 
plants  this  one  place,  with  only  an  insignificant  force  of  men,  may 
send  as  many  cases  of  occupational  poisoning  to  the  physicians 
as  all  the  rest  put  together.  This  is  when  the  DNB  is  allowed  to 
flow  out  and  solidify  in  open  pans  or  on  a  filtrose  bed,  and  then  is 
broken  up  and  shoveled  or  scooped  up  into  trucks  or  barrels. 

The  best  arrangement  of  this  kind  seen  allows  the  product  from 
the  nitrators  to  flow  into  a  covered  hot  washing  tank  with  an  air 
exhaust,  then  out  into  a  cold-water  tank  outside  the  building  under 
a  shed,  where  it  is  pelleted  by  the  cold  water.  This,  then,  is  caT-' 
ried  by  a  screw  conveyor  to  the  barrels.  The  worst  one  seen  had 
admittedly  so  much  poisoning  among  the  DNB  men  that  sometimes 
it  seemed'  as  if  the  plant  must  shut  down  for  want  of  help.  The 
nitrated  product  ran  out  into  open  pans  and  solidified  there;  the 
men  then  broke  up  the  solid  mass,  shoveled  the  fragments  into 
trucks,  and  emptied  them  into  a  crystallizer,  heated,  where  the 
DNB  was  melted  and  crystallized.  This  was  inclosed.  The  crys- 
tallized DNB  was  then  screened,  and  although  the  screen  was  in- 
closed a  fine  powder  escaped  in  quantities  when  the  screened  prod- 
uct was  poured  into  barrels  through  a  canvas  chute,  for  this  leaked 
badly.  Near  the  screen  stood  open  barrels  of  lumpy  DNB,  which 
had  been  dug  out  of  the  crystallizer  through  an  opening  and  which 
was  fed  into  the  screen  with  a  shovel. 

In  a  German  plant  visited  in  the  summer  of  1919  the  DNB  is 
never  transported  in  the  open;  it  is  melted  and  blown  through 


PROCESSES    VJ   DYE    MANUFA(JTUHE.  53' 

pipes.  When  it  is  packed  a  false  cover  is  used,  with  two  openings — 
one  connected  with  the  hopper  of  DNB,  the  other  with  tlie  dust- 
collecting-  sj^stem.  In  this  way  all  dusty  shoveling  and  scooping 
and  all  direct  contact  are  avoided.  Even  the  packed  and  closed 
barrels  are  regarded  as  a  source  of  possible  danger,  for  DNB 
volatilizes  at  ordinary  temperature,  and  still  more  on  a  hot  day; 
so  the  Germans  store  these  barrels  in  an  open  shed,  lest  the  fumes 
from  them  affect  men  working  in  that  department. 

4,  Reduction. — Acid  reduction  is  carried  on  with  the  aid  of  hydro- 
chloric acid  and  iron  filings;  alkaline  reduction,  vv^ith  zinc  dust  and 
usually  caustic  soda;  neutral  reduction,  with  zinc  dust  alone.  The 
former  is  used  in  the  production  of  anilin  from  nitrobenzene^, 
ortho  and  para  toluidin  from  nitrotoluene,  alpha  naphthylamine 
from  nitronaphthalene.  It  is  also  used  in  the  reduction  of -dinitro- 
benzene  to  phenylendiamine,  dinitrotoluene  to  toluylendiamine,  ni- 
tronaphthodisulphonic  acid  to  amidonaphthodisulphonic  acid,  nitro- 
phenol  to  amidophenol,  and  so  on.  Since  reduction  begins  with  a 
nitro  compound  and  ends  with  an  amido  compound^  it  follows  that 
there  is  a  decided  risk  in.  connection  with  the  reaction,  a  risk  more 
or  less  recognized  and  more  or  less  guarded  against  in  every  plant. 
When  the  process  goes  forward  normally,  without  any  hitch,  there  is 
little  trouble  with  sickness  among  the  men.  To  be  sure,  the  taking 
of  samples  from  time  to  time,  if  carelessly  done  so  that  the  liquid 
spills  on  the  hands,  may  give  rise  to  mild  poisoning  or  fairly  serious, 
according  to  the  compound  undergoing  reduction,  and  in  hot,  heavy 
weather,  especially  on  the  night  sliift,  the  fumes,  which  escape  from, 
the  feed  hole,  may  cause  enough  discomfort  to  force  a  man  to  quit 
work  for  that  shift  though  he  is  able  to  return  for  the  next  one. 
But  frequent  and  serious  cases  of  acute  poisoning  and  a  general  con- 
dition of  anemia  among  the  men  in  the  reduction  department  is 
found  only  when  the  mechanical  arrangements  for  reduction  are 
faulty.  It  is  when,  for  some  reason,  poor  construction  of  the  reducer, 
poor  charging,  failure  of  motive  power,  or  some  other  defect,  the  iron 
filings  fall  and  cake  around  the  paddles  and  the  reaction  has  to  be 
interrupted,  the  manhole  oj^ened,  and  the  "  sludge  "  cleaned  out  for 
a  fresh  start,  it  is  then  that  serious  poisoning  occurs.  There  is  a 
wide  variation  between  anilin  reduction  departments  in  different 
plants,  it  being  a  matter  of  ordinary  observation  that  while  in  some 
of  them  the  caking  of  a  reducer  is  a  rare  accident,  which  may  not 
happen  oftener  than  once  in  three  months,  in  others  it  seems  to  be 
an  ordinary  occurrence.  The  first  kind  of  a  plant  has  a  scrupulously 
clean  reduction  department,  v/ith  only  a  slight  odor  of  anilin,  or, 
l^erhaps,  it  is  quite  free  from  odor;  the  second  is  an  untidy,  some- 
times filthy,  spot,  the  floor  covered  with  a  wet  mass  of  black  iron 
filings,  which  are  tracked  over  the  floor  by  the  men's  feet ;  the  anilin 
water  runs  partly  through  the  gutters  in  the  floor,  but  some  of  it 
spreads  over  and  lies  about  in  pools.  The  men  work  through  the 
open  manhole,  prodding  the  caked  mass  with  iron  rods  and  hoes  and 
then  drag  it  out.  Their  hands  and  clothing  show  the  contact  with 
this  anilin-laden  sludge,  which  their  work  necessitates.  In  such  a 
]Dlace  anilin  poisoning  is  looked  upon  as  a  serious  thing  and  one  very 
hard  to  control,  while  in  well-managed  plants  it  is  considered  a 
rarity  unless  in  very  slight  form. 


54  IlNDL'STRIAL  POISOXIXG   I^n"    MAKIISTG   COAL-TAE   DYES. 

In  the  reduction  of  dinitrobenzen©  to  plienylendiamJn&  the  danger 
is  much  greater  than  in  reducing  mononitrobenzene  to  aniiin,  and, 
unless  the  charging  is  done  with  great  care 5  trouble  inevitably  re- 
sults sooner  or  later.  This  is  also  true,  although  to  a  less  extent,  with 
the  reduction  of  dinitrotoiuene  to  toluylendiamine.  The  English  and 
the  Germans  know  mueh  more  about  the  dangers  of  these  compounds 
than  \vd  do  and  use  special  precautions  in  handling  them.  A  good 
device  for  charging  the  reducer  Avitli  dinitrobenzene  was  seen  in  an 
English  factory.  The  covered  truck  had  an  opening  just  on  a  level 
with  the  feed  door  of  the  reducer,  and  when  the  lid  of  this  opening 
was  dropped  dowm^it  formed  a  bridge  between  truck  and  reducer 
over  Vv^hich  the  I>KB  could  be  pushed  without  scooping  or  dropping. 
In  contrast  to-  this  was  the  method  used  in  one  of  the  American 
plants  visited,  where  the  I>NB  was  shoveled  from  an  open  truck 
into  a  pail  and  this  dumped  into  the  reducer.  It  is  impossible  for 
a  man  doing  work  like  that  to  keep  from  contact  with  the  stuff,  and, 
aside  from  the  contact,  there  is  the  continual  volatilization. 

In  making  phenylendiamine  by  rednction  of  D2iB  in  one  Ameri- 
can plant  there  was  much  poisoning  among  the  men  so  long  as  the 
product  was  filtered-  hot,  but  this  has  been  avoided  by  sending  in  a 
stream  of  coM  water  wliich  rjrerents  fumes  from  the  filter  press  and 
also  from  the  sluclge.  The  sludge  contains  only  1  per  cent  of  DiVTB, 
but  enough  to  give  trouble  if  it  is  hot. 

•  The  usual  dangers  of  acid  reduction  are  well  known  and  under- 
stood, but-  there  is  one  possible  danger  in  connection  with  it  and  stiil 
more  in  connection  with  alkaline  reduction,  which  is  not  generally 
recognized  in  American  plants,  although  it  has  long  been  known  in 
Germany  and  has  recently  attracted  a  good  deal  of  attention  in 
Englancl.  This  is  the  evolution  of  fumes  of  hydrogen  arsenide, 
spoken  of  in  the  former  section  of  this  report. 

There  are  several  processes  in  dye  manufacture  in  which  the  con- 
ditions may  occur  which  give  rise  to  the  formation  of  hydrogen 
arsenide,  namely,  the  contact  of  an  arsenic -bearing  metal,  zinc  or 
iron,  with  hydrochloric  acid  or  sulphuric,  or  the  contact  of  an  arsenic- 
bearing  acid  with  one  of  these  metals.  In  one  of  the  cases  reported 
from  England  a  plumber  went  into  an  emjDty  acid  tank  to  repair  it. 
That  is,  "the  tank  was  technically  empty,  it  had  been  washed  out 
and  only  about  a  bucketful  of  fluid  was  left  at  the  bottom.  But 
the  acicf^  chamber  acid,  contained  enough  arsenic  to  poison  him  and 
he  died  of  hemorrhagic  nephritis  two  days  later.  A  similar  but  even 
more  disastrous  accident  took  place  not  long  ago  in  iSew  Jersey. 
Here  three  men  went  into  an  iron  tank  that  had  contained  chamber 
acid  but  was  supposed  to  be  empty  and  clean.  All  were  quickly 
overcome  by  fumes  of  AsH,  and  two  died  from  its  effects.  It  does 
not  take  much  arsenic  in  this  form  to  cause  severe  poisoning.  Ac- 
cording to  Eambousek  an  amoimt  corresponding  to  about  one-hun- 
dredth of  a  milligram  of  arsenic  is  sufficients 

The  ether  sources  of  hydrogen  ar-senide  in  the  dye  indn^try  are 
reduction  processes,  both  acid  and  alkaline.  In  reducing  niti'obehzene 
to  aniiin,  nitrotoluene  to  toluidin,  etc.,  this  gas  may  be  given  oft"  and 
therefore  it  is  dangerous  to  send  cleaners  or  pipe  fitters  _  into  the 
reelucer,  aside  from'the  danger  of  the  nitro  and  amido  bodies. _  The 
arsenic  may  be  contained  in'the  iron  but  is  more  likely  to  be  in  the 


PROCESSES    11^   DYE    MAKUFACTUEE.  55 

acid.  One  English  manager  said  that  he  had  had  four  men  on  sick 
leave  at  once  as  a  result  of  such  an  accident  as  this.  The  same  risk 
must  be  thought  of  in  connection  with  the  reduction  of  nitro  to 
amido  naphthosiilphordG  acid. 

But  it  is  especiaiiy  in  tlae  making  of  benzidin,  as  this  is  done 
in  Engiish  plants  and  in  some  American  plants,  that  precautions 
against  arsine  poisoning  must  be  taken,  for  it  is  here  that  a 
large  number  of  English  workmen  have  recently  been  found  to  be . 
suffering  from  mild  or  severe  poisoning.  This  method  of  making 
benzidin  is  as  follows:  Nitrobenzene  is  reduced  to  hydrazobenzene 
by  m.eans  of  zinc  dust  and  caustic  soda.  One  of  the  Home  OiSce 
experts  believes  that  at  this  point  hydrogen  arsenide  may  be  given 
off,  but  the  industrial  chemists  are  skeptical.  There  is  no  doubt, 
however,  as  to  the  danger  of  the  next  stage,  when  h3KlroehlorLc  aeicl 
is  used  to  dissolve  out  the  zinc  dust  and  leave  hydrazobenzene.  This 
process  must  be  carried  out  in  the  cold,  for  otherwise  some  of  the 
hydrazobenzene  might  be  converte-d  to  benzidin,  pass  into  solution 
and  be  lost,  and  therefore  it  is  customarj/  in  these  factories  to  open 
up  the  acidifying  tub  and  drop  eliunks  of  ice  into  the  acid.  This 
is  the  point  at  which  the  accidents  have  usually  arisen,  for  if  arsenic 
is  present  in  the  zinc  dust,  or  in  the  acid,  there  majr  be  a  sudden 
evolution  of  AsH,  when  they  meet  and  the  liqaiid  may  "  boil  over," 
as  the  men  say.  Usually  the  zinc  is  the  substance  at  fault  in  the  most 
serious  accidents,  for  the  acid  .seldom  carries  as  m.ueh  arsenic  as  may 
be  carried  by  the  zinc.  Since  the  latter  is  in  powder  form,  th© 
conditions  are  ideal  for  the  production  of  the  gas ;  and  since  the  tub 
must  be  opened  to  admit  the  ice,  its  escape  is  easy. 

The  next  stage  is  also  attended  with  some  danger,  and  here,,  too, 
cases  of  poisoning  have  developed.  The  contents  of  the  tub  with 
the  zinc  chloride  in  solution  and  the  crystals  of  hydrazobenzene  are 
sent  into  a  filter  press  and  if  AsHg  is  present,  bubbles  may  be  given 
off  from  the  liquid  and  from  the  paste.  In  one  of  these  English 
plants  it  was  evident  that  just  this  had  happened  and  the  chemist 
in  charge  spoke  with  much  emphasis  of  the  necessity  of  providing 
good  drains  under  the  filter  press  and  thoroughly  flushing  the  floor 
from  time  to  time,  never  letting  any  of  the  fluid  lie  about  in  pools. 
He  said  that  the  use  of  compressed  a-ir  to  blow  out  the  filter  press 
was  an  advantage  also  because  this  served  to  carry  off  whatever 
fumes  might  be  left.  In  the  last  stage,  when  the  hydrazobenzene 
is  heated  to  boiling  by  steam  to  convert  it  into  benzidin,  it  is  ipos- 
sible  that  some  unchanged  azobenzene  may  be  given  off  with  the 
steam  and  this  compound  is  decidedly  poisonous. 

In  consequence  of  the  accidents  vfhich  have  occurred,  the  English 
factory  inspectors  r^re  insisting  on  changes  in  the  equipment  of  ben- 
zidin departments,  provision  of  fume  pipes  for  the  reduction,  acidi- 
fying, and  final  conversion  pans,  proper  drains  for  the  filter  presses, 
and  so  on.  In  one,  the  management  has  put  in  a  long  sluiceway  to 
the  manhole  of  the  acidifying  pan,  with  a  valve  at  the  end  and  the 
ice  is  sent  down  this  sluice  by  the  workmen,  who  can  tlius  stand  at 
a  distance  from  the  manhole,  too  far  to  inhale  whatever  fumes  mig*ht 
escape.  This  was  the  plant  that  had  the  most  trouble  in  its  ben- 
zidin department.  In  another,  the  cases  of  hydrogen  arsenide  i^oi- 
soning  had  occurred  in  connection  with  the  reduction  of  nitro  to 
amido  naphthosulphonic  acid  and  since  then  they  have  used  arsenic- 


56  IXDUSTEI.IL   POISOXIXG   IX    MAKIXG   COAL-TAE   DYES. 

free  acid  (contact  acid)  for  this  reaction,  but  even  so  the  iron  may 
contain  arsenic,  so  they  test  the  fumes  from  time  to  time  Trith  mer- 
curic  chloride  paper. 

This  way  of  making  benzidin  is  rather  crude  and  is  not  used  in 
our  largest  plants.  It  is  perfectly  possible  to  produce  the  proper 
degree  of  cold  by  means  of  brine  coils  and  so  avoid  the  opening  of 
the  acidifier  for  ice.  This  is  done  in  one  of  our  plants.  It  does  not, 
however,  do  away  with  the  risk  of  escaping  fumes  if  for  any  other 
reason  the  manhole  is  opened  or  if  there  is  a  leak,  nor  does  it  pre- 
vent fumes  at  the  filter  press,  nor  the  risk  of  poisoning  the  men  who 
repair  or  clean  the  acidifying  kettle.  The  process  in  use  in  the  bet- 
ter American  plants  does  not  require  the  use  of  acid  and  is  quite  free 
from  any  danger  of  arsenic  at  any  stage.  By  this  method  the  zinc 
dust  is  not  changed  to  the  chloride  and  dissolved  out,  but  is  sepa- 
rated by  passage  through  a  very  fine  screen  which  catches  the  crys- 
tals of  Iwdrazobenzene  and  lets  the  dust  through. 

In  smaller  American  plants  the  procedure  may  be  the  same  as  that 
in  England,  and  carried  on  without  any  precautions.  In  going 
through  the  records  of  a  hospital  in  a  i^ew  Jersey  town,  histories  of 
two  men  poisoned  while  on  a  night  shift  were  found;  both  were 
made  very  ill,  and  one  of  them_  died  some  three  weeks  later."  They 
had  been  employed  in  a  plant  which  was  making  napthionic  acid 
from  alphanaphthylamine  and  sulphuric  acid,  and  also  benzidin 
base  and  sulphate  by  the  process  just  described.  The  company  had 
installed  a  fume  pipe  but  had  never  completed  it  and  it  was  never 
used.  According  to  the  information  obtained,  the  men  in  the  hos- 
pital were  two  out  of  five  affected  on  the  same  night  shift  by  some 
gases  of  unknown  nature.  The  diagnosis  given  was,  very  naturally, 
"  anilin  or  alphanaphthylamine  poisoning." 

Quite  different  dangers  attend  reduction  by  means  of  sodium  sul- 
phide as  in  the  making  of  sulphur  dye  intermediates.  Paranitro- 
phenol  is  reduced  to  paraamidophenoL  picric  acid — which  is  trini- 
trophenol — is  reduced  to  picramic  acid — amiclo-dinitro  phenol — by 
means  of  sodium  sulphide,  and  if  the  reaction  is  acid,  fumes  of  hy- 
drogen sulphide  may  be  given  off. 

In  m^aking  1-2-4  amidonaphthosulphonic  acid,  reduction  and  sul- 
phonation  are  brought  about  simultaneously  by  the  use  of  sodium 
sulphide  and  sulphuric  acid  and  here  the  fumes  of  sulphur  dioxide 
may  be  bad. 

5.  Chlorincttion: — The  introduction  of  the  chlorine  atom  may  take 
place  in  the  benzene  ring  or  in  a  side  chain.  The  resultixig  product 
may  be  inert,  or  highly  poisonous,  or  it  may  resemble  closely  the 
nonchlorinated  compound,  as  anilin  hydrochloride  differs  from  ani- 
lin only  in  being  a  solid  instead  of  a  liquid.  The  escape  of  fumes  of 
hydrochloric  acid  used  for  the  production  of  chlorine  gas  and  of  the 
gas  itself  constitute  a  danger  and  it  is  always  necessary  to  provide 
a  vent  or  an  absorbent  chamber  for  the  gas,  which  is  best  taken  up 
in  water  and  neutralized.  It  is  especially  in  the  making  of  anilin 
hydrochloride  and  of  nigrosin  that  these  fumes  are  troublesome. 
The  use  of  cylinder  chlorine  in  the  manufacture  of  pyrone  dyes  is 
hardly  ever  troublesome,  for  only  small  quantities  are  needed. 

6.  AJJcylation. — This  consists  in  the  introduction  of  methyl  or 
ethyl  groups  into  a  hydroxy  or  amido  gi'oup.     The  important  ex- 

«  See  page  45, 


PKOCESSES   ISr   DYE   MANUFACTURE.  57 

nmples  of  this  class  of  compounds  are  dimethylanilin  and  diethylani- 
lin.  The  hitter  is  made  by  treating  anilin  with  ethyl  alcohol.  Di- 
methylanilin maA'  be  made  by  the  action  of  methyl  alcohol  or  methyl 
chloride  on  anilin  under  heat  and  pressure,  or  by  the  action  of  di- 
methyl sulphate  without  pressure.  The  trade  poisoning  that  has 
occurred  in  the  usual  processes  of  a,lkylation  is  to  be  attributed  to  the 
anilin  rather  than  alkyl  derivatives,  which  are  less  toxic.  When  di- 
methyl sulphate  is  used  for  methylation,  a  new  danger  is  introduced 
which  has  already  been  discussed. 

In  making  methjdanilin,  some  trouble  has  been  experienced  from 
the  methyl  alcohol  used.  Methyl  alcohol  is  also  employed  to  bring 
about  alkylation  of  fuchsin  to  form  other  triphenylmethane  colors, 

7.  Oxidation. — The  substances  used  as  oxidizers  are  usually  in- 
organic salts,  such  as  sodium  dichromate,  sodium  chlorate,  or  per- 
manganate, manganese  dioxide,  lead  peroxide  with  a  mineral  acid. 
Anthraquinone,  the  intermediate  for  alizarin  dyes,  is  produced  by 
oxidizing  anthracene  with  sodium  dichromate.  In  making  fuchsin, 
orthonitrotoiuene  maj^  be  used  as  an  oxidizer,  or  mononitrobenzene. 
In  this  case,  fumes  from  these  compounds  must  be  guarded  against. 
The  use  of  sodium  and  potassium  dichromate  has  led  to  serious 
chrome  ulcers  in  England,  but  apparently,  from  the  literature,  it  is 
in  using  it  as  a  mordant  that  the  trouble  is  encountered,  not  in  the 
production  of  dyes.  Certainly  in  the  United  States  chrome  ulcers 
are  practically  unknown  in  alizarin  dye  works.  Nor  does  the  use  of 
red  lead  seem  to  give  rise  to  enough  lead  poisoning  to  make  itself 
known.  Oxidation  may  result  in  the  production  of  poisonous  qui- 
nones,  and  this  is  a  clanger  not  generally  recognized. 

8.  Car'boQ:'yJation. — This  is  generally  effected  hy  the  action  of 
caustic  soda  and  pure  carbon  dioxide  gas  upon  a  phenol  as  a  result  of 
which  the  COOTI  group  is  introduced  into  the  ring.  For  instance, 
carboxylation  of  phenol  yields  salicjdic  acid,  which  is  much  used  in 
the  dye  industry.  This  process  is  not  so  dangerous  as  caustic  fusion, 
because  it  does  not  require  nearly  so  much  free  alkali  and  the  result- 
ing compound  is  less  poisonous  than  the  original  compound. 

9.  Liming. — Lime  or  chalk,  or  som.etimes  caustic  lime,  may  be 
added,  usually  to  a  sulphonated  product  to  separate  one  salt  from 
another.  For  instance,  in  the  production  of  betanaphthol  the  sepa- 
ration of  the  alphanaphthalene  sulphonic  acid  from  the  beta  is 
brought  about  by  adding  lime,  because  the  lime  salt  of  the  alpha 
acid  is  very  soluble  in  cold  water  and  that  of  the  beta  acid  is  only 
slightly  so. 

10.  Condensation. — This  process  consists  in  the  union  of  two  com- 
pounds, or  two  molecules  of  the  same  compound  to  form  a  new  com- 
pound by  the  loss  of  Avater  or  HCl  or  H3N.  Sometimes  hydro- 
chloric or  sulphuric  acid  is  used  with  phosphorus,  zinc,  sulphur,  or  tin 
to  bring  about  this  reaction.  There  is  no  special  danger  involved  ex- 
cept in  the  liberation  of  the  volatile  substances  if  the  apparatus  is 
faulty,  or  in  the  case  of  accident  allowing  the  workmen's  hands  or 
clothes  to  become  splashed  with  such  a  substance. 

11.  Diazotizing  and  coupling. — An  amido  compound  on  treatment 
with  nitrous  acid  (sodium  nitrite  and  hydrochloric  acid  are  gener- 
ally used)  yields  a  compound  called  diazo.  This  is  then  coupled  with 
an  aromatic  amine  or  phenol  to  form  an  azo  compound.     Although 


58  IXDUSTHIAL   TOISO'Si:SG   IS"    MAKIXG    CO^iL-TAE   DYES. 

tiie  compounds  that  are  diasotized  are  tosic  the  fact  that  the  reaction 
of  diazotizing  or  coupling  is  carried  on  in  the  cold  lessens  very  much 
the  danger  of  both  fumes  and  contact.  An  instance  of  the  many 
dj-cs  that  are  made  in  this  -way  is  chrome  brown,  which  is  made  by 
diazotizing  piepa^^ic  acid  (dinitroamidophenol)  and  coupling  with 
betana-phthoL 

The  making  of  intermediates  is  on  the  whole  attended  with  m^ore 
risk  of  poisoning  than  the  making  of  finished  colors,  and  the  benzene 
intermediates  are  much  more  dangerous  than  the  naphthalene  and 
anthracene  intermediates.  Toluene  and  xylene  are  included  with 
benzene  in  this  statement. 

COLOR  MAKUFACTUSE. 

The  aso  dyes  are  made  with  a  primarv  amine,  anilin  or  toluidin  or 
toluylendiamine  or  benzidin  or  some  similar  body,  which  is  treated 
with  nitrous  a^id  in  the  cold.  The  diazo  compouncl  produced  is  then 
coupled  with  an  aromatic  amine  or  phenol  to  form  a.n  azo  compound. 
Diazotizing  is  done  a;t  about  zero,  centigrade.  The  making  of  azo 
dyes  is  the  safest  branch  of  the  color  indu.stry.  a,nd  a  plant  which 
does  not  ma,ke  its  awn  intermediates  and  makes  only  azo  dyes  may 
probably  be  kept  practically  free  from  occupational  disease.  Typi- 
cally, the  work  is  carried  on  in  one  high  building  with  three  levels, 
the  coupling  tanks  into  which  the  intermediates  are  blown  being  on 
the  top  level,  so  that  whatever  fume  escapes  is  taken  care  of  up  there 
and  does  not  contaminate  the  air  on  the  other  levels.  It  is  said  that 
if  the  sodium  nitrite  used  for  diazo  production  is  riui  in  too  quickly 
nitrous  fumes  may  be  given  oE. 

Antlvroxene  dyes  may  be  produced  also  without  much  risk  of 
trouble.  The  most  important  of  these  dj^es  is  alizarin,  wliich  is 
synthetic  madd«r.  To  produce  this,  antliracene  is  oxydized  usually 
with  potassium  or  sodium  bichromate  to  anthracfuinone,  and  this  is 
sulphonated  and'  then  fused  with  caustic  soda  and  chlorate  of  potash 
to  form_  alizarin;  or  dioxj^anthraquinone.  Indanthrene  is  produced 
from  anthracene  by  oxidation  to  antliraquinone,  sulphonation,  amida- 
tion  (vidth  ammonia  and  catahiiic  copper),  caustic  fusion.  Indan- 
threne blue  is  formed  by  air  oxielation ;  greens  and  violets  are  pro- 
duced by  the  use  of  chlorine  gas,  nitrobenzene,  and  nitric  acid.  Ob- 
viously, there  are  decided  risks  in  the  making  of  indanthrene  colors, 
espc<;iaily  from  chlorine,  nitrous  fumes,  and  nitrobenzene,  for  al- 
though during  the  uninterrupted  reaction  no  fumes  may  escape-,  any 
accidental  interference  with  the  process,  and  these  are  not  unconmion, 
may  result  in  a  very  bad  state  of  things.  Benzanthrene  causes 
dermatitis. 

Indigo-  is.made  in  tliree  large  plants  which  were  visited^  the  process 
differing  slightly  in  each.  In  two,  formaldehyde  and  anilin  are  used 
and  sodium  cyanide  is  either  added  to  or  formed  in  the  course  of  the 
reaction.  In  the  course  of  this  ammonia  fumes  may  be  given  off. 
This  reaction  is  followed  by  hydrolysis,  usually  with  caustic  potash, 
to  phenylglycine.  It  is  in  the  filtering,  dryings  and  transporting  of 
phenylglvcine  that  most  of  the  illness  am^ong  the  workmen  occurs. 
It  is  a  ver^^  light  and  fiuff^^  powder,  and  althou^jh  it  is  usually  said  to 
contain  no  more  than  1  per  cent  of  anilin,  it  may  set  up  very  serious 


COLOR   MANUFAGTUEE.  59 

acute  and  chronic  anilism  if  unusual  precautions  are  not  taken,  espe- 
cially in  emptying  the  filters  and  drying,  dumping,  transporting, 
and  barreling  the  powder. 

In  the  third  plant  anilin  and-monochloracetic  acid  are  used  to  form 
phenyiglycine.  During  this  process  the  fumes  that  are  given  off 
contain  anilin,  hydrochloric  acid,  and  chlorine.  Monochloracetic  acid 
is  strongly  caustic. 

In  one  of  the  three  plants  the  filter  press  stands  in  a  separate 
building,  which  is  really  a  shed,  with  ample  ventilation.  While  the 
air  is  being  blown  through  the  press  the  vapor  is  bad,  but  usually  it 
is  not  necessary  to  have  anyone  inside  the  shed  at  that  time.  The 
presses  are  then  opened,  the  crystals  dumped  and  scraped  up  and 
shoveled  into  barrels.  For  this  work  rubber  aprons,  gloves,  and 
respirators  are  provided.  From  the  filter  the  crystals  go  to  a  tank 
with  caustic  potash,  the  temperature  being  kep>t  as  low  as  possible 
to  prev^ent  too  much  ammonia  fumes.  A  second  filtration  to  remove 
dirt  follows,  and  then  evaporation  in  an  inclosed  badger.  The 
liquor  falls  over  great  hot  metal  rolls,  on  which  a  thin  layer  of  pow- 
der forms,  which  scrapes  o&  and  falls  into  a  box.  The  powder  is 
kept  from  flying  about  by  heavy  canvas  curtains.  This  dryer  is  in 
a  separate  room  with  a  high,  windowed  roof,  and  only  one  operator 
works  on  each  shift.  He  is  required  to  spend  all  but  15  minutes  of 
each  hour  in  a  little  sheltered  porch  just  outside  the  room,  for  it  is 
extremely  dusty,  and  everything  is  covered  vfitli  white  powder  like 
a  flour  mill.  Tie  is  given  gloves  ar-,d  a  respirator.  Boxes  of  the 
powder  go  to  the  next  room,  and  are  emptied  into  a  barrel  packer 
of  a  good  mechanical  type,  but  nevertheless  there  is  a  great  c'eal  of 
white  powder  in  this  room. 

The  second  plant  has  a  better  method.  The  phenytglycine  is  evap- 
orated in  a  vacuum  dryer,  and  a  traveling  screw  carries  the  drj  pow- 
der to  an  inclosed  hopper,  from  which  it  falls  into  a  barrel,  stand- 
ing underneath.  A  canvas  chute  connects  hopper  and  barrel,  and 
there  is  an  exhaust  with  an  opening-  right  beside  the  top  of  the  barrel. 
At  the  time  when  visited  no  dust  v/as  visible  anywhere  around  this 
apparatus. 

The  third  plant  was  very  bad.  The  synthetic  indigo  department 
was  well  housed  in  a  great  new  building,  amply  ventilated  for  or- 
dinary purposes,  but  the  air  was  full  of  fumes  and  dust,  so  that  a 
short  stay  there  was  enough  to  affect  one's  head  quite  noticeably. 
Two  of  the  men  at  work  there  were  quite  livid,  one  of  them  start- 
lingly  so. 

The  di  and  tri  yhenylmetliane  dyes  are  often  called  anilin  dyes, 
others  are  called  toluiclin  dyes.  The  intermediates  used  are  deriva- 
tives of  benzene,  toluene,  and  xylene,  and  there  is  probably  more 
typical  nitro  and  a.mido  poisoning  in  connection  with  this  class  of 
dyes  than  any  other.  The  onl}^  diphenylm_ethane  color  of  importance 
is  auramine,  in  the  course  of  the  manufacture  of  which  strong  fumes 
of  ammonia  may  be  given  off,  and  also  sulphuretted  Iiydrogen,  The 
waste  water  from  the  auramine  building  may  carry  a  good  deal  of 

The  triphenylmethane  dyes  are  very  important,  and  require  the 
use  of  large  quantities  of  nitrobenzene,  nitrotoluene,  anilin,  the  tolui- 
dins,  especially  para,  the  anisidins  and  methyl  and  ethyl  cbrivatives 


60  IXDrSTEI.U.  POISOXIXG   IX    MAKIXG    CO/O.-TAE   DYES. 

of  anilin.  The  malachite  green  series  belong  in  this  group.  Mala- 
chite green  is  made  from  benzaldehj^de  and  dmiethjdanilin,  Vic- 
toria green  from  benzaldehvde  and  diethylanilin.  Fuchsin,  the 
starting  point  for  so  many  colors,  is  made  with  anilinhydrochloride, 
or  formaldehyde,  ortho  and  para  toluidin  and  anilin  oil.  This  forms 
Trhat  is  called  the  "  red  oil  mix."'  If  formaldehyde  is  used  instead 
of  anilin  hydrochloride  there  is  risk  of  a  boil  over,  and  this  may  also 
happen  Trith  anilin  hydrochloride  if  it  is  added  too  fast.  The  red 
oil  mix  is  oxydized  with  nitrobenzene  or  orthonitrotoluene  and 
'•  fuchsm  melt ''  is  formed.  This  department  is  frequently  men- 
tioned in  German  factory  inspection  reports  as  the  place  in  which 
a  case  of  intoxication  occurred.  The  fuchsin  melt  is  treated  with 
caustic  soda  to  make  fuchsin  base,  and  this  is  phenolated  by  means 
of  anilin  and  benzoic  acid  to  opal  bhie,  oil-soluble,  which  is  changed  by 
sulphonation  to  water-solu]:)le  alkali  blue.  Fuchsin  can  also  be  alkj^- 
lated  to  other  colors  of  this  same  group  by  displacement  of  the  H 
atoms  in  the  amido  nucleus  by  ethyl  or  methyl  groups,  but  it  is 
simpler  to  start  with  an  alkjdated  amine.  For  instance,  methyl  violet 
can  be  made  with  dimethylanilin,  sodium  chloride  and  chloride  of 
copper,  cresol  and  phenol,  and  then  treatment  with  hydrogen  sulphide. 

Eosins  and  f.uoresceiris  are  closety  alKed  to  the  so-called  "  anilin  " 
dyes  (the  tripheyhnethane  dyes),  and  are  sometimes  classified  with 
them,  sometimes  called  p^^rone  ctyes,  sometimes  resorcin  dyes.  Chlo- 
rine, bromine,  and  iodine  are  used,  also  fuming  sulphuric  acid  and 
caustic  soda,  but  the  gases  are  provided  in  cylinders  and  not  enough 
are  used  to  give  any  trouble. 

Nigrosin  and  indidln  are  made  by  melting  anilin  and  nitrobenzene, 
ferric  chlorid  and  hydrochloric  acid.  This  "melt"  is  ground,  then 
washed.  Fumes  of  anilin  and  of  hydrochloric  acid,  especially  of  the 
latter,  may  be  quite  heavy  in  these  departments. 

The  nitro  or  nlfroso  dj'es  are  in  them.selves  poisonous.  It  is  only 
recently  that  a  man  in  Germany  was  poisoned  by  handling  aurantia, 
which  is  hexanitrodiphenylamine.  The  greatest  risk  of  industrial 
poisoning,  however,  is  in  the  manufacture,  which  involves  nitration 
processes  and  the  possible  escape  of  nitrous  fiunes.  Aside  from 
aurantia,  the  best -known  nitro  colors  are  picric  acid,  trinitrophenol, 
and  Martins  yellow  or  dinitronaphthol,  and  naphthol  yellows. 

There  is  probably  more  risk  of  occupational  poisoning  in  the 
making  of  sulphur  dyes  than  any  other  class  of  colors,  for  the 
introduction  of  sulphur  and  sodium  sulphide  may  result  in  the 
liberation  of  sulj^huretted  hvdrogen  fumes.  The  preparation  and 
use  of  the  intermediates  also  involve  exposure  to  compounds  which 
have  decidedly  toxic  properties,  and  set  up  not  only  very  trouble- 
some skin  eruptions  but  systemic  poisoning  as  well.  For  instance, 
chlorbenzene  is  nitrated,  during  which  process  nitrous  fiunes  may  be 
given  off.  The  resulting  ortho  and  para  nitroclilorbenzene  must  be 
separated,  the  para  crystals  from  the  ortho  liquid.  This  operation 
was  seen  done  in  an  open  centrifuge,  and  although  the  centrifuge  was 
in  a  small  comi^artment  with  a  strong  suction  fan  drawing  away  the 
fumes,  it  was  necessary  to  provide  a  current  of  fresh  air  directly 
beside  the  man  who  was  obliged  to  go  in  from  time  to  time  and 
empty  the  centrifuge.  Even  with  these  precautions  the  vapors  were 
strong  beside  the  centrifuge.     The  paranitrochlorbenzene  is  washed 


PRETENTION   or   OCCUPATIONAL  POISONING.  61 

and  saponified  to  paranitroplienol,  which  is  a  prolific  source  of 
dermatitis  unless  it  is  handled  with  great  care.  Reduction  of  para- 
nitroplienol to  paraamidophenol  is  done  for  sulphur  blue.  For 
sulphur  black,  dinitrochlorbenzene  is  used,  and  the  production  and 
use  of  this  compound  in  the  early  days  of  American  dye  manufacture 
gave  rise  to  so  much  distressing  skin  disease  as  to  necessitate  changes 
in  method  or  it  would  have  been  impossible  to  keep  the  men  at  work. 

Sulphur  browns  and  yellows  result  from  the  treatment  of  phenyl- 
endiamine  with  sulphur  and  benzidin.  Phenylendiarnine  results 
from  the  reduction  of  paranitranilin,  one  of  the  most  dangerous  of 
the  nitro  and  amido  compounds  made  from  anilin  through  acetanilid 
and  paranitracetanilid.  The  process  of  saponifying  or  hydrolizing 
paranitracetanilid  is  often  attended  with  the  liberation  of  fumes. 

Primulin  is  made  from  paratoluiclin,  which  is  fused  with  sulphur 
to  a  "  melt,"  then  ground  and  sulphonated.  Sulphuretted  hydrogen 
is  sometimes  evolved  in  making  the  melt  and  a  typical  case  of  tolui- 
din  poisoning  was  reported  in  a  man  who  was  in  charge  of  the  mak- 
ing of  the  melt. 

The  danger  from  fumes  of  hydrogen  sulphide  is  greatest  in  the 
manufacture  of  khaki  and  sulphur  browns  and  yellows,  less  in  con- 
nection with  sulphur  black,  and  very  slight  in  making  sulphur  blue. 
As  a  usual  thing  an  effort  is  made  to  burn  the  H2S  to  a  mixture  of 
sulphur  oxides.  In  one  plant  powerful  suction  carries  HgS  to  an  iron 
column  where  it  is  absorbed  by  caustic  soda. 

PREVENTION  OF  OCCUPATIONAL  POISONING. 

It  is  true  in  the  anilin  dye  industry,  as  in  every  American  industry, 
that  no  generalizations  can  be  made  about  the  protection  that  is 
given  to  the  workmen  against  the  dangers  inherent  in  his  occupation. 
This  differs  widely,  not  only  in  completeness  but  in  character.  In 
one  plant  the  emphasis  will  be  placed  on  rigid  cleanliness  of  the 
premises  and  removal  of  fumes,  while  less  stress  will  be  laid  on  the 
medical  department.  In  another  there  is  much  less  effort  made  to 
prevent  the  men  from  coming  in  contact  with  different  toxic  com- 
pounds, but  there  is  a  very  complete,  admirably  equipped  plant  dis- 
pensary. It  seems  that  no  American  plant  as  yet  has  developed 
both  these  sides  as  thoroughly  as  possible,  although  one  of  the  older 
companies  has  come  very  near  it. 

Perhaps  it  may  be  well  to  begin  the  consideration  of  the  care 
which  should  be  given  to  anilin  dye  workers  by  a  description  of  the 
methods  used  in  some  of  the  German  factories.  That  of  Meister, 
Lucius  &  Briining,  in  Hoechst,  was  described  as  follows  by  Grand- 
homrne  back  in  1880.  At  that  time  this  factory  employed  1,000 
men,  40  superintendents,  and  25  chemists.  It  manufactured  anilin 
colors;  resorcin  colors  (eosins)  ;  naphthol  colors,  yellows,  reds,  and 
browns;  and  alizarin  colors.  The  buildings  were  one-storied  with 
saw-tooth  roofs,  the  windows  in-  the  roof  being  kept  open.  Fumes 
were  carried  off  in  underground  flues;  the  floors  were  of  brick  laid 
in  cement,  impermeable  to  moisture,  and  furrowed  with  many  cement- 
lined  gutters  to  carry  off'  fluids.  In  all  rooms  where  steam  or  other 
vapors  were  formed  the  walls  were  whitewashed  twice  a  year.  Each 
room  had  at  least  one  large  door  to  the  outside,  usually  two.     In  the 


62  liS'DUSTSIAI.   POISOSrilTG  IIST    MAKING   GOAL.-TAV,   DYES. 

anilin  department  e^'erjching  was  inclosed.  Tlie  sludge  was  driven 
out  with  compressed  air  and  discharged  through  pipes  to  a  distant 
field  where,  after  thorough  drying,  the  iron  was  recovered. 

In-  the  factory  inspection  report  for  1910-11  a  description  is  given 
of  tlie  welfare  work  in  the  Aktiengesellschaft  liir  Aniiinfabiikation. 
The  plant  dispensary  held  clinics  twice  a  da;/,  with  two  physicians 
and  two  nurses.  There  were  also  two  visiting  nurses  for  the  work- 
men's families.  The  bathhouse  was  available  for  the  use  of  the 
families  twice  a  week.  There  was  an  infant  welfare  station,  and 
milk  was  provided  at  cost.  Free  care  was  given  in  a  maternity 
home  to  the  women  employees  and  the  wives  of  the  worlonen  during 
confinement  and  for  three  weeks  after.  The  mother  V\''as  given  3  to 
5  marks  a  week  if  she  nursed  her  baby.  There  were  illustrated 
lectures  on  hygiene,  and  the  medical  cars  included  light  baths, 
electric  treatnientSy.  vibrations,  massage,  ultra-violet  rays.  Coifee  was 
l^rovicled  free,  and  also  milk  if  the  man  would  pledge  himself  to 
drink  no  alcohol  during  work  time.  The  report  states  that  "  anilism ; 
has  been  practically  abolished  by  a  closed  system  for  mixing,  grind-, 
ing,  transporting,  and  for  producing  nitro  and  amido  compounds ;" 
by  excellent  ventilation,  scrupulous  cleanliness  and  rigid  insistence 
on  baths." 

Koelsch,  one  of  the  principal  authorities  on  industrial  hygiene  in 
Germany,  gives  the  following*  acb/ice  to  manufacturers  of  anilin 
d^^es  and  intermediates:  Medical  examination  must  be  made  of  aE 
applicants  for  work,  and  men  must  be  rejected  who  are  weakly, 
anemic,,  or  with  aiiections  of  heart  or  kidneys.  Nobody  under  20 
years  of  age  or  over  50  should  be  accepted.  Persons  with  sldn  dis- 
eases should  be  rejected,  and  i^  is  better  not  to  employ  women  be- 
cause of  their  greater  tendency  to  hemorrhage  and  because  of  the 
possible  effect  on  their  offspring.  The  hours  should  not  be  too 
long.  He  adidses  alternation  of  employment  unless  the  ideal  can 
be  attained  of  a  selected  force  of  trained  and  immune  workers,  it 
IS  important  to  prevent  heat  and  humidity  as  much  as  possible,  for 
experience  shows  that  there  is  always  more  poisoning  on  hot,  wind- 
less days,  and  the  same  condition  is  brought  about  by  allowing  steam 
•to  escape  into  the  workroom. 

The  rules  in  force  should  be  made  to  fit  the  different  compomids. 
It  is  not  necessary,  for  instance,  to  make  the  men  Avorking  with  the 
toluene  compounds  bathe  daiJy  and  have  a  clean  suit  of  working 
clothes  every  clay.  He  believes  that  medical  inspection  for  these 
VAen  need  not  come  oftener  than  once  in  six  or  eight  weeks,  and 
there  is  no  reason  why  they  should  not  work  10  or  12  hours.  For 
men  working  vfith  benzene  compounds  far  greater  precautions 
must  be  taken.  They  must  have  proper  working  clothes  and  caps, 
frequently  changed :  they  must  bathe  daily ;  they  should  not  work 
more  than  six  hours,  and  in  hot  weather  this  period  should  be  di- 
vided, three  hours  in  the  earl}^  morning  and  three  in  the  late  after- 
noon. It  is  very  important  to  provide  thick,  impervious  footwear 
nnd  to  see  that  the  feet  are  kept  clean,  especially  if  the  man  per- 
spires much.  Koelsch  objects  to  gloves,  especially  if  the  work  is 
greasy,  for  their  use  simply  results  in  keeping  the  hands  in  more 
intimate  contact  with  the  substance  to  be  avoided  than  they  would 
be  if  no  gloves  were  used.     It  is  wrong  to  place  dependence  upon 


PiiEVSHTIOI-r    OF    OCCUPATIOl'^AL,   P0IS02n"I;n"G.  QS 

respirators;  dusfc  anel  fiimes  must  be  removed  at  the  point  of  origin, 
No  ePttiiig  m  workrooms  sliouid  be  allowed,  and  it  is  well  to  provide 
a  big  cup  of  hot  coffee  at  the  end  of  the  day's  work. 

In  case  of  poisoning,  Koelscli  advises  removing  the  man  to  fresh 
air,  butnot  walking  liim  up  and  down.  He  must  be  made  to  lie 
doAvn.  His  clothes  must  be  removed  and  he  must,  be  given  a  thor- 
ough bath.  If  there  is  dyspnea,  oxygen  inhalation  with  artificiai 
respiration  is  advised.  If  there  is  marked  blood  destruction,  it 
may  be  well  to  bleed  and  give  saline  injections,  but  this  is  not  nec- 
essary if  the  pulse  is  good.  Make  the  man  drink  abundance  of  milk 
or  hot  black  coifee  or  weak  tea,  and  give  him  mild  laxatives.  During 
convalescence  give  hirn  milk,  iron,  and  arsenic,  but  no  alcohol. 
Cursclimann  insists  on  the  value  of  cool  sponging  or  douches  as  a 
stimulant  to  heart  and  respiration.  He  also  advises  the  adminis- 
tration of  abundant  quantities  of  milk. 

In  a  large  Grerman  dye  works  visited  in  July,  1919,  the  preven- 
tion of  occupational!  poisoning  had  been  carried  to  a  much  higher 
point  than  that  seen  elsewhere.  It  is  not  extravagant  to-  say  that 
the  passageways  between  buildings  and  the  roadwaj^s  through  the 
grounds  were  cleaner  than  are  the  floors  in  some  American  factories. 
There  was  no  odor  anywhere.  One  could  not  have  guessed  what 
was  being  produced  in  the  amlin  reduction  room.  It  was  explained 
that  each  depa.rtment  was  under  the  charge  of  a  chemist  who  was 
responsible  for  all  the  sickness  occurring  there,  i^o  fluid  was  ever 
allowed  to  drip  or  spill  on  the  floor.  If  an  accidental  case  of  poison- 
ing should  occur,  the  chemist  would  be  called  to  account,  not  be- 
fore the  heads  of  the  plant,  but  before  a  committee'  of  the  associated 
anilin  industries,  the  "Berufsgenossenschaft,"  for  it  is  they  who 
have  to  j>?ij  the  sickness  compensation,  and  they  make  a  strict  in- 
quiry into  everj^  case.  This  system  seems  to  result  in  a  more  rigid 
control  of  the  sources  of  industrial  accident  and  disease  than  is  ob- 
tained when  each  establishment  carries  its  own  insurance  and  is  alone 
responsible  for  the  ca-ses  which  occur  in  it.  Naturally  an  associa- 
tion of  ail  the  members  of  a  branch  of  industry  can  exert  pressure 
upon  one  member  which  will  result  in  a  more  careful  supervision  on 
the  part  of  the  chemists  and  physicians  than  is  to  be  expected  vdien 
what  happens  in  the  plant  is  known  only  to  that  one  plant  and  the 
loss  falls  onh'  on  it.  Merely  to  save  hi&  face  and  avoid  the  disagree- 
able experience  of  examination  at  the  hands  of  his  colleagues  the 
man  in  charge  will  do  all  he  can  to  keep  off  accidents  and  accidental 
poisoning.  After  all,  the  criticism  of  one's  own  class  is  the  criticism 
most  to  be  dreaded,  and  it  is  probable  that  the  influence  of  the 
"Berufsgenossenschaft"  is  more  potent  than  the  authority  of  the 
factory  inspection  deT>artment. 

The  freedom  from  odors  and  the  striking  cleanliness  of  the  plant 
were  the  result  of  this  strict  supervision.  No  apparatus  which  was 
wet  with  any  sort  of  fluid  was  placed  on  the  floor.  Near  the  opening 
of  the  manhole  of  each  kettle  or  autoclave  was  a  smooth  metal  shelf 
upon  which  the  workman  was  instructed  to  lay  any  wet  piece  of  ma- 
chinery as  well  as  the  lid  of  the  manhole.  The  chemist  in  charge  was 
responsible  for  the  cleanliness  of  this  metal  shelf.  All  vapors,  even 
plain  steam,  were  removed  by  fume  pipes,  which  could  be  connected 
up  with  the  air  exhaust  system,  and  always  before  opening  an  auto- 


64  INDUSTRIAL  POISOITIIsrG   IIST   MAKIlsTG   COAL-TAE-  DYES. 

ciave  or  kettle  the  exhaust  must  be  turned  on  and  left  on  so  long  as  the 
receptacle  was  open.  It  was  explained  that  this  rule  was  based 
on  exj)erience,  for  in  processes  of  this  kind  it  is  impossible  to  be  sure 
of  all  the  reactions,  and  the  only  safe  thing  is  to  guard  against  the  pos- 
sible esca.pe  of  such  fimies  as  hydrogen  arsenide  and  hydrogen  sul- 
phide. 

The  dust  prevention  was  excellent,  every  effort  being  made  to  catch 
even  the  color  dust,  so  that  the  men  engaged  in  color  packing  showed 
very  little  color  on  their  clothes  and  faces.  The  small  packages  were 
filled  under  glass  and  an  exhaust  jorovided  at  that  point.  Barrel 
packing  was  done  in  the  open  room,  but  through  a  lid  with  two  open- 
ings, one  connected  with  the  dust  recovery  system  and  the  other  with 
a  hoj)per  containing  the  ground  color. 

This  particular  German  factory  had  a  lavish  supply  of  basins  and 
showers,  1,200  for  3,000  men,  and  also  several  bath  tubs.  It  is  not 
compulsory  in  Germany  for  the  employer  to  provide  overalls  for  the 
men,  but  in  this  place  good  two-piece  suits  of  blue  denim  were  pro- 
vided, mended,  and  laundered.  At  the  end.  of  three  to  six  months,  ac- 
cording to  the  process  in  which  the  man  was  em^^loyed,  a  new  suit 
was  provided  and  the  old  one  given  to  the  man  for  his  own.  The  guide 
said  that  this  inclined  the  man  to  take  good  care  of  his  overalls.  The 
men  employed  there  are  decidedlj^  high-grade  workmen,  as  is  shown 
by  one  little  significant  item — the  a^bsence  of  doors  to  the  lockers. 
The  locker  room  has  open  compartments  for  the  men's  street  clothing, 
one  for  each  man.  It  was  said  that  it  was  much  more  healthful  to 
let  the  clothing  air  and  dry  than  to  shut  it  up  behind  doors,  and  that 
there  was  no  clanger  of  the  men  stealing  each  other's  clothing. 

The  new  applicants  for  employment  in  Germany  are  examined  by 
a  physician  and  doubtful  cases  rejected,  but  there  seems  to  be  at  pres- 
ent no  routine  examination  of  the  working  force,  such  as  is  carried 
on  in  England  and  in  some  American  i^lants.  All  cases  of  occupa- 
tional illness  are  strictly  investigated,  as  explained  above. 

The  rules  for  the  control  of  the  dye  industry  in  Great  Britain  are 
those  which  vrere  passed  in  1908,  but  the  factory  inspection  depart- 
m^ent  of  the  Home  Office  is  preparing  a  new  code  which  will  be  more 
detailed  and  comprehensive.  Already  the  local  inspectors  have  issued 
orders  supplementing  the  rules  of  1908  as  new  dangers  came  to  light 
with  the  great  increase  of  the  industry.  On  the  whole,  the  construc- 
tion and  management  of  the  British  plants  is  about  on  a  level  with  the 
American,  if  one  leaver  out  of  consideration  our  worst  specimens.  As 
is  invariably  true  in  every  industry  studied,  the  United  States  con- 
tains some  factories  which  are  dirtier  and  more  neglected  than  any  in 
England.  This  is  partly  because  of  the  arming  standards  for  factory 
inspection  in  our  different  States.  The  provision  of  working  clothes 
for  the  men  in  the  English  factories  is,  as  it  is  in  ours,  sometimes 
ample,  sometimes  inadequate.  The  provision  of  washing  facilities  in 
the  best  English  factories  is  quite  as  lavish  as  in  the  best  American, 
but  the  worst  is  not  nearlj^  so  bad  as  our  worst.  Shower  baths  are 
required  in  England,  but  at  least  one  American  dye  works  which 
manufactured  phenol  during  the  war,  is  noAV  manufacturing  dye  inter- 
mediates as  well  as  dyes,  and  employs  2,000  men,  has  not  a  single 
shower  bath. 

No  American  dye  works  has  yet  reached  the  point  of  doing  every- 
thing possible  to  protect  the  workers  from  the  dangerous  compounds 


PREVENTION   OF   OCCUPATIONAL  POISONING.  65 

which,  are  used  or  produced,  or  which  may  be  accidentally  evolved  in.  | 
the  course  of  production.  The  faults  in  these  plants  depend  in  the 
first  place  on  the  construction  of  the  buildings  and  here,  curiously 
enough,  some  of  the  newest  are  most  at  fault.  Of  two  factories  ob- 
served, one  has  been  running  for  years  and  is  situated  in  a  large  city ; 
the  other  is  hardly  more  than  two  years  old  and  is  out  in  the  country, 
with  practically  unlimited  space  to  spread  over.  The  first  is  excellent 
in  construction,  the  buildings  are  high  and  well  ventilated,  the  floors 
of  concrete  or  some  similar  substance,  properly  drained.  The  second 
consists  of  small  buildings,  often  with  low  ceilings,  huddled  together 
so  that  they  shut  off  light  and  air  from  each  other,  the  floors  are 
chiefly  of  wood  already  rotting  and  roughened,  and  the  walls  and 
windows  look  as  if  the  plant  were  20  years  old  instead  of  2. 

Even  if  the  construction  is  good,  the  method  of  carrying  on  the 
different  processes  may  result  in  a  continual  leakage  of  vapors  or 
fluids,  or  dusts,  or  the  frequent  need  for  repairs,  which  always  means 
imtidiness  and  sometimes  a  dangerous  state  of  affairs.  To  compare 
two  anilin  reduction  plants :  In  one,  the  smooth  concrete  floors  are 
clean  and  dry;  the  high  ceiling  and  open  windows  insure  good  air 
because  the  only  source  of  fumes  is  the  occasional  taking  of  a  sample 
or  perhaps  a  puff  from  the  feed  opening.  The  sludge  is  run  out  into 
the  open  and  the  reducers  do  not  have  to  be  opened  and  cleaned  out 
oftener  than  about  once  in  three  months.  In  the  other  plant  the 
notes  taken  at  the  time  of  the  visit  read  as  follows :  "  The  reduction 
building  is  dirty,  and  it  is  plain  that  there  is  a  good  deal  of  trouble 
with  the  working  of  the  apparatus.  It  seems  to  be  a  common  occur- 
rence to  have  a  reducer  stop  and  then  the  iron  falls  on  the  paddles 
and  cakes  them,  and  they  have  to  be  dug  out.  They  take  certain  pre- 
cautions to  lessen  the  danger  of  this  work ;  they  drive  in  steam,  but 
it  is  admitted  that  the  steam  can  reach  only  the  upper  layers  of  the 
iron  filings,  and  as  soon  as  the  man  begins  to  dig  he  reaches  the 
anilin.  One  reducer  had  Just  been  opened  up  because  the  iron  was 
caked,  and  the  door  at  the  bottom,  about  4  feet  by  2^,  was  open.  A 
man  must  climb  in  through  this  door  to  finish  the  cleaning,  and  al- 
though he  is  allowed  to  stay  in  only  10  minutes,  it  is  admittedly  a 
bad  job,  for,  of  course,  he  can  get  very  thoroughly  smeared  with 
anilin  sludge  in  that  time.  Another  reducer  had  just  been  cleaned 
out.  The  sludge  from  the  two  lay  in  heaps  on  the  floor  and  little 
rivulets  of  anilin  water  ran  from  the  heaps.  The  fumes  were  quite 
strong,  although  the  building  is  big  and  high  and  well  provided  with 
windows.  According  to  the  physician,  there  is  trouble  every  time  a 
reducer  is  cleaned  out,  even  though  compressed  air  is  driven  in  while 
the  man  is  at  work  inside.  Various  improvements  were  discussed, 
such  as  making  an  opening  in  the  bottom  of  the  reducer  and  passing 
in  an  air  hammer  to  break  up  the  caked  filings  and  then  running  the 
sludge  out  with  water,  but  it  seems  obvious  that  what  they  need  is 
some  way  of  keeping  the  paddles  of  the  reducers  running  and  pre- 
vent caking." 

The  cleanliness  of  the  plant  also  depends  on  the  standards  of  the 
men  in  charge.  This  sounds  like  a  truism,  but  it  is  really  worth 
repeating.  There  are  perhaps  two  plants  among  those  visited  in 
which  one  can  go  dry  shod  through  every  department,  but  it  is  need- 

25431°— 21 5 


66  IXDUSTPJAL  POISONING  IN  MAKING   COAL-TAR  DYES. 

less  to  say  that  this  is  an  exception  and  that  ordinarily  one  must  be 
prepared  to  Trade  through  jxiddles  on  ahnost  all  the  ground  floors. 
The  statement  is  commonly  made  that  most  of  the  cases  of  anilin 
poisoning  come  from  the  anilin  Tvater  that  has  soaked  through  the 
men's  boots,  and  several  superintendents  have  said  Tvith  pride  that 
they  provide  Tvooden-soled  boots  for  their  men.  It  seems  not  to 
have  occurred  to  them  to  try  to  provide  dry  floors  instead. 

In  German  factories  the  rule  seems  to  be  to  prevent  the  escape  of 
any  fumes  or  vapors,  no  matter  how  harmless — a  rule  based  upon  long 
experience.  In  the  TTnited  States  each  factory  seems  to  be  acquiring 
its  oTvn  experience,  rather  at  the  expense  of  the  -workmen.  If  a  case 
of  sickness  develops  in  connection  with  a  given  process,  the  matter 
is  investigated  more  or  less  promptly,  and  the  dangerous  fumes  are 
prevented,  not  always  immediately,  but  eventually.  In  a  few  rare 
instances  the  scientific  knowledge  which  is  so  abundantly  available 
in  these  factories  has  been  taken  advantage  of  and  those  fiunes  which 
are  known  to  be  poisonous  are  carried  off  by  suction,  even  though 
there  may  never  have  been  an  actual  ease  of  poisoning  from  them  in 
that  i)lant. 

In  Great  Britain  the  centralized  control  and  the  presence  of  ex- 
perts in  the  factory  inspection  department  make  it  possible  to  apply 
in  all  the  factories  the  experience  which  has  been  gained  in  one.  For 
instance,  the  occurrence  of  hydrogen  arsenide  poisoning  in  one  ben- 
zidin  department  resulted  in  precautions  being  installed  against  such 
an  accident  in  all  the  other  works  which  made  benziclin. 

The  actual  care  taken  of  the  individual  workman  differs  very 
widely  in  our  American  dye  factories.  The  matter  of  2)roviding 
Avorking  clothes  for  the  men  is  admittedly  important,  for  all  prac- 
tical men,  as  well  as  physicians,  know  that  these  poisons  are  absorbed 
through  the  skin,  and  that  clothing  impregnated  with  a  nitro  or 
amido  compound  acts  like  a  poisonous  poultice.  Yet  one  of  the 
largest  plants  in  the  country,  employing  over  1,200  men  in  process 
work  and  laboratory  work,  has  never  made  any  provision  of  overalls 
for  the  men,  althoiigh  the  safety  expert  says  that  plans  have  been 
made  to  do  so.  Another  plant  for  the  manufacture  of  intermediates 
and  dyes  employs  2.000  men  and  provides  neither  overalls  nor  ade- 
quate Vashing  facilities.  In  contrast  to  this  are  several  factories 
where  the  provision  is  ample  and  generous.  In  one  large  plant  clean 
clothes  are  provided  for  the  DXB  and  DXT  men  daily :  for  the  anilin 
men  twice  a  week.  A  plant  making  printer's  inks  and  em]:)loying  380 
men  provides  not  only  the  usual  denim  overalls  but  clean  underwear, 
shirts,  socks,  and  heavy  boots  with  wooden  soles  an  inch  and  a  quarter 
thick.  The  clothing  is  repaired  and  two  suits  a  week  are  provided. 
In  the  paranitranilin  department  of  another  plant,  since  closed,  the 
men  were  given  underwear  as  well  as  overalls  and  socks,  a  clean 
supply  every  day.  These  men  were  required  to  bathe  at  the  end  of 
the  day's  work,  and  if  any  man  was  engaged  in  an  unusually  dusty 
job  he  was  made  to  bathe  as  soon  as  it  was  over  and  change  all  his 
clothes.  One  of  the  oldest  plants,  and  probably  the  cleanest  of  all, 
which  employs  between  1,500  and  1.600  men,  supplies  working  clothes, 
but  makes  the  men  pay  for  the  first  suit.  The  process  men  have  a 
clean  suit  every  other  day.  unless  after  a  cleaning  or  repairing  job, 
in  which  case  they  change  at  once.  Color  men  wear  theirs  until  they 
are  badly  torn  or  worn  out. 


PREVENTION    OF    OCCUPATIONAL   POISONING.  67 

There  is  a  decided  difference  of  opinion  as  to  the  wearing  of  gloves. 
Some  foremen  hold  that  the  men  get  on  much  better  without  them 
when  working  in  nitro  and  amido  compounds;  that  it  is  impossible 
to  prevent  leaks,  and  a  leaking  glove  is  much  worse  than  none  at  all. 
They  maintain  that  the  men  are  much  better  protected  if  they  are 
encouraged  to  wash  their  hands  frequently  during  the  day  than  they 
are  by  wearing  gloves.  This  can,  of  course,  be  done  only  if  there  is 
a  supply  of  hot  water  and  soap  in  the  department  itself,  which  is  not 
always  the  case.  No  experienced  man  depends  on  respirators  to  pro- 
tect his  employees  from  poisoning.  To  exhibit  with  pride  a  collec- 
tion of  rubber  sponge  respirators  is  a  mark  of  inexperience.  On  the 
other  hand,  an  abundant  supply  of  warm  water  at  different  points  in 
the  plant  is  an  evidence  of  experience.  Even  if  warm  water  can  not 
be  provided,  there  must  be  a  supply  of  cold  water  readily  acces- 
sible in  every  department  where  caustics  are  handled,  or  where  the 
mineral  acids  are  handled,  for  severe  burns  can  be  prevented  only  by 
j^rompt  and  thorough  washing  with  water. 

The  great  majority  of  American  dye  works  have  good  and  well 
equipped  wash  rooms  and  bathrooms  and  shower  baths  for  their 
process  men.  This  is  required  by  law  in  the  States  in  which  most 
of  these  plants  are  situated  (Massachusetts,  New  York,  New  Jersey, 
Pennsylvania,  Illinois) ,  but,  unfortunately,  it  seems  not  to  be  required 
in  Wisconsin.  Usually  soap  or  some  washing  powder  is  also  pro- 
vided ;  less  often,  towels.  There  is  a  great  difference  in  the  degree  to 
which  the  employees  of  the  different  plants  avail  themselves  of  these 
facilities.  For  instance,  in  one  factory  90  per  cent  of  the  men  use 
the  shower  baths ;  in  another  only  25  per  cent.  The  difference  prob- 
ably comes  back  to  the  personality  of  the  welfare  manager,  or  per- 
haps of  the  individual  foreman. 

It  is  not  so  important  in  this  industry  to  provide  against  the  men 
eating  their  lunch  in  their  workrooms  as  it  is  in  connection  with  lead 
work.  Nevertheless  it  is  desirable  to  have  rooms  provided  in  which 
no  work  is  carried  on,  and  in  which  hot  food  or  at  least  hot  drinks 
may  be  bought  by  the  employees.  Factories  which  are  situated  far 
from  town  are  usuall}^  obliged  to  have  a  cafeteria  for  the  men,  but 
the  provision  is  not  as  general  as  it  should  be,  and  the  whole  matter 
of  proper  feeding  of  the  process  men  should  be  taken  more  seriously 
than  it  is  in  American  factories. 

Much  more  attention  is  paid  in  Europe  to  the  proper  feeding  of 
men  in  all  the  dangerous  trades  than  is  true  over  here,  and  in  the  dye 
industry  it  is  recognized  that  a  poor  dinner  and  an  inadequate 
breakfast  may  have  an  important  influence  on  industrial  poisoning 
among  those  employed.  The  English  have  long  laid  stress  on  the 
necessity  for  proper  feeding  in  the  lead  trades,  and  they  have  now 
applied  the  same  principles  to  the  coal-tar  industries.  They  look 
on  the  dinner  pail,  so  common  in  our  factories,  as  distinctly  bad, 
with  its  cold,  soggy  sandwiches  and  pie.  A  hot  digestible  meal  in 
the  middle  of  the  day  or  night  is  considered  essential,  and  therefore 
all  these  plants  are  provided  with  kitchens,  simply  but  sufficiently 
equipped  with  a  stove  for  boiling  water  for  tea  and  an  oven  to  keep 
food  hot.  Opening  one  of  these  ovens,  one  finds  them  filled  with 
bowls  of  meat  and  vegetable  stew,  or  the  meat  pie  the  English  are  so 
fond  of.    If  they  wish,  the  men  may  bring  a  rasher  of  ham  or  bacon 


68  INDUSTRIAL  POISONING  IN   MAKING   COAL-TAR  DYES. 

and  a  couple  of  eggs  and  have  them  cooked  at  noon.    All  day  long  tea 

may  be  brewed,  and  it  is  customary  to  allow  10  or  15  minutes  in  the 
middle  of  the  afternoon  for  this;  sometimes  also  in  the  middle  of 
the  morning.  Xobody  can  deny  the  refreshing  and  restful  effect  of  a 
cup  of  hot  tea  with  milk  and  sugar  in  the  course  of  the  afternoon. 
Aside  from  the  other  effects  of  indigestion,  one  must  not  forget  that 
it  lessens  elimination  of  a  poison,  makes  it  harder  for  the  system 
to  rid  itself  of  what  has  been  absorbed. 

The  conviction  that  industrial  poisoning  is  greatly  facilitated  by 
poor  and  insufficient  breakfasts  has  made  these  English  employers 
provide  milk  for  their  workers  in  the  morning  as  soon  as  they  go  on. 
A  pint  apiece  is  the  allowance,  and  it  is  given  free.  The  Germans  are 
not  so  liberal  since  the  war,  but  they  provide  hot  coffee  in  the  morn- 
ing and  afternoon,  coffee  and  soup  at  noon,  for  one-tenth  the  usual 
price.  Hot  milk  as  an  antidote  for  anilin  poisoning  holds  a  high 
place  in  English  estimation.  One  manager  said  he  had  treated  a  man 
overcome  from  having  his  hands  in  anilin  water — he  was  a  bricklayer 
and  had  mixed  his  mortar  with  wash  water  that  had  a  little  anilin  in 
it — by  pouring  hot  milk  and  porridge  down  his  throat  till  the  man 
could  hold  no  more.  Hot  coffee  with  milk  is  also  used  and  is  doubt- 
less a  good  stimulant  in  such  cases. 

There  is  one  American  factory  which  gives  the  men  in  the  dinitro- 
benzene  dej)artment  all  the  milk  they  will  drink. 

The  need  for  continual,  careful  medical  supervision  in  the  manu- 
facture of  dyes  and  intermediates  is  greater  now  than  it  will  be  in  a 
few  years'  time,  for  so  long  as  the  industry  is  still  new  and  unfamiliar, 
so  long  as  it  is  still  in  the  experimental  stage,  it  will  be  necessary  to 
have  the  men's  physical  condition  constantly  under  the  observation 
of  a  doctor  experienced  in  detecting  the  early  signs  of  intoxication. 
All  of  the  American  plants  employing  large  forces  of  men  have  some 
medical  service,  not  always  adequate,  but  some  of  the  smaller  ones 
dispense  with  medical  supervision  altogether.  A  plant  in  Massa- 
chusetts employing  90  men  has  not  even  a  part-time  doctor.  As  for 
the  larger  ones,  it  would  be  hard  to  explain  the  difference  one  finds 
in  the  proportion  of  doctors  and  nurses  to  the  numbers  employed  in 
the  different  plants.  Certainly  it  does  not  depend  on  the  compara- 
tive dangers  nor  on  the  cleanliness  or  filthiness  of  the  premises.  In 
a  dye  and  chemical  works  employing  1.600  men  there  are  three  nurses 
and  one  part-time  doctor.  In  another  employing  1,600  men  there 
are  five  nurses  and  one  full-time  doctor  with  an  assistant.  A  plant 
with  2,000  men  manages  to  get  on  with  the  services  of  one  doctor 
for  two  hours  daily,  one  nurse,  and  one  ^dsiting  nurse,  while  another 
with  the  same  number  of  men  has  five  full-time  physicians  and  seven 
men  nurses. 

It  must  be  remem.bered  that  a  large  part  of  the  physician's  tune, 
sometimes  almost  all  of  it.  is  taken  up  with  the  examination  of  new 
applicants  for  work,  so  that  unless  he  has  ample  assistance,  he  has 
little  time  to  give  to  the  very  necessary  work  of  protecting  the  men 
who  are  actually  employed.  The  enactment  of  workmen's  compensa- 
tion laws  in  the  different  States  has  made  the  employer  feel  that  he 
must  protect  himself  against  claims  for  j)hysical  disabilities  which 
possibly  may  have  been  present  when  the  man  entered  his  employ- 
ment, and  therefore  he  insists  on  this  preliminary  examination.    That 


PREVENTIOlSr    OF    OCCUPATIONAL   POISONING.  69 

this  may  involve  an  enormous  amount  of  medical  work  can  be  seen 
by  the  record  of  one  plant  in  which  420  to  470  new  men  are  examined 
each  month  in  order  to  keep  up  a  force  of  2,000. 

There  are  several  companies  that  maintain  a  high  standard  of 
medical  work.  This  means  that  the  physician  does  not  confine  him- 
self to  office  work,  but  makes  frequent  trips  through  the  plant, 
familiarizing  himself  with  the  various  processes,  and  learning  just 
where  the  dangers  are.  Routine  blood  examinations  are  made  of 
men  who  are  in  the  more  dangerous  processes  and  who  show  slight 
signs  of  poisoning,  and  a  fall  in  hemoglobin  is  the  signal  for  sus- 
pension from  work.  In  connection  with  this  it  is  well  to  remember 
that  the  usual  method  of  estimating  hemoglobin  does  not  give  satis- 
factory results  when  the  blood  has  a  brownish  tint,  for  then  it  is  diffi- 
cult to  match  it  up  with  the  color  standard. 

It  should  be  a  rule  to  suspend  from  process  work  any  man  whose 
hemoglobin  is  as  low  as  85  per  cent,  and  not  to  return  him  to  process 
work  till  he  has  gained  at  least  5  per  cent.  Sometimes  extravagant 
claims  are  made  by  industrial  physicians  with  regard  to  the  improve- 
ment of  men  under  treatment.  One  physician  said  that  a  man  whose 
hemoglobin  had  been  98  per  cent  when  he  was  employed  and  had 
fallen  to  7'2per  cent,  as  a  result  of  acute  poisoning,  had,  under  treat- 
ment, brought  his  hemoglobin  back  to  91  per  cent  in  four  days,  the 
treatment  consisting  in  light  outdoor  work  and  proper  food.  This 
seems  perhaps  not  impossible,  but  certainly  unexpectedly  rapid.  As 
a  usual  thing  the  return  to  a  normal  hemoglobin  content  is  slow.  Of 
course  the  man  should  always  be  removed  from  contact  with  the 
poison,  but  it  is  not  enough  for  the  doctor  to  order  him  out  of  doors. 
Sometimes  the  outdoor  job  is  heavier  and  more  fatiguing  than  his 
former  work,  and  he  is  only  telling  the  truth  when  he  comes  to  the 
doctor  complaining  that  he  feels  worse  than  he  did  when  he  was  on 
his  own  job. 

The  question  of  rejections  is  very  unportant.  The  procedure  car- 
ried on  in  one  large  dye  works  already  referred  to  is  recommended — 
that  is,  a  careful  classification  of  work  according  to  the  risks  in- 
volved. Here  the  men  accepted  for  employment  are  assigned  to  one 
of  the  three  classes  of  occupations,  according  to  the  doctor's  findings. 
The  blood  pressure  is  taken  and  an  examination  is  made  of  the  urine 
as  well  as  the  usual  physical  examination.  Men  with  slight  abnor- 
malities are  not  admitted  to  the  more  dangerous  work,  nor  are  any 
men  under  18  or  over  48  years  of  age.  This  classification  also  permits 
the  doctor  to  shift  a  man  from  a  dangerous  job  into  a  safe  one  with 
ease.  It  must  be  remembered  that  the  mechanical  department  often 
contains  the  most  dangerous  work  of  all,  cleaning  and  repairing,  and 
that  these  men  are  usually  less  on  their  guard  against  dangerous 
compounds  than  are  the  process  men,  because  they  are  not  familiar 
with  the  nature  of  the  compounds  with  which  they  come  in  contact. 


APPENDIXES. 


APPENDIX  1.— STRUCTURE  OF  THE  BENZENE  RING  AND  ITS  PRIN- 
CIPAL DERIVATIVES,  ISOMERIC  FORMS,  ETC. 

The  benzeue  molecule  is  for  convenience  represented  by  a  "  ring  "  or  hexagon 

CH 


HC 


which,    if    unmodified,    stands    for    CgHg,    or 


HC 


CH 


CH 


Usually  the  carbon 


CH 


and  hydrogen  elements  in  a  graphic  formula  are  not  written  out,  for  it  is 
understood  that  all  replacements  for  the  formation  of  new  compounds  take 
place  at  the  expense  of  the  hydrogen  atoms  and  that  no  matter  how  compli- 
cated a  series  of  such  replacements  may  be,  the  original  6  carbon  atoms  of 
the  ring  remain  unaltered.    To  illustrate,  the  formula  for  picric  acid,  trinitro- 

HO 


NOo 


phenol,  is  usually  written  thus. 


the  unoccupied  angles  of  the  hexagon 


NO2 


NO2 


are  iTUderstood  to  be  taken  by  the  original  hydrogen  atoms. 

Benzene  is  CeHe.     Toluene  is  methyl-benzene,  CeHsCHs.     Xylene  is  dimethyl 
benzene,  C6H4  (CH3)2.    The  graphic  formulas  are  these: 

CHi  CH3 

/\  /\,  /\oH 


In  naphthalene  two  benzene  rings  are  joined  directly  together,  at  the  ex- 

c 
pense  of  two  hydi-ogen  atoms,  which  results  in  the  formula  CioHg  or 

Anthracene  is  three  such  rings  joined  together,  or  C14H10. 


Phenanthrene  has  the  same  number  of  atoms  as  anthracene  and  its  formula 
is  also  CnHio,  but  the  three  rings  are  differently  grouped. 


70 


APPENDIX  1. 


71 


When  the  hydrogen  of  the  benzene  ring  is  displaced  by  HO,  phenols  result : 
06H6+HO=CoH5HO,  hydroxybenzene,  or  phenol  or  carbolic  acid. 
C6Ho-|-2  HO=C6H4(HO)2.  dihydroxybenzene  or  resorcin. 
CoHo+3  HO=C6Hs(HO)3,  trihydroxybenzene  or  pyrogallic  acid. 
CoH5CH3+HO=C6H4CH3HO,  hydroxy  toluene  or  cresol. 

The  introduction  of  the  nitro  group  into  the  ring  produces  nitro  compounds, 
such  as  nitrobenzene,  C0H5NO2,  and  dinitrobenzene,  CoH4(N02)2;  nitrotoluene, 
C6H4CH3NO2,  and  trinitrotoluene,  C6H20H3(N02)3;  nitronaphthalene,  CioH-NO.., 
and  dinitronaphthol,  OioH5HO(N02)2. 

Reduction  of  a  nitrocojupound  changes  the  NO2  radical  to  NH2  and  produces 
auiido  compounds.  From  nitrobenzene  conres  amidobenzene  or  anilin,  CgHsNHo. 
From  dinitrobenzene,  diamidobenzene,  or  phenylendiamine,  CeH4(NH2)2.  From 
nitrotohiene  comes  amidotoluene  or  toluidin,  CflH4CH3NH2.  From  nitroxylene 
comes  amidoxylene  or  xylidin,  CsHs  ( CH3 )  2NH2.  The  reduction  may  be  partial, 
as  when  dinitrobenzene  is  reduced  to  nitrauilin,  thus : 

NO2  NH, 


N02 


\/ 


N02 


and  this  may  be  further  hydrolyzed  to  nitrophenol ; 

HO 


NO 


\/ 


and  then  reduced  to  amidophenol : 


HO 


NH2 


For  convenience  the  angles  of  the  benzene  hexagon  have  been  numbered  in 
the  order  of  the  figures  on  the  face  of  the  clock. 


When  only  one  hydrogen  atom  is  replaced  by  a  new  atom  or  radical  it  is 
no  importance  which  of  the  six  is  replaced,  but  when  m'ore  than  one  is  sub- 
stituted several  so-called  isomers  or  isomeric  forms  are  produced,  bodies  which 
have  the  same  number  of  the  same  atoms,  but  are  differently  grouped  and 
differ  decidedly  from  each  other  in  physical  properties  and  in  toxicity.  For 
instance  there  are  three  xylenes,  or  dimethylbenzenes,  C6H4(CH3)2. 


CH3 


CH3 


CHs 


Orthoxylene. 


;CH3 
Metaxylene. 


CH3 


CH3 
Paraxylene. 


72 


I27DUSTFJAL   POISOXING  IX   MAKING   COAL-TAE   DYES. 


There  are  tliree  cliliycli'oxybenzenes,  C6H4(HO)2. 

HO  HO 


HO 


\/ 


JHO 


meta,  orresorein. 


HO 


HO 
para,  or  hydroquinone. 


ortho,  or  pyrocatechin. 
CH3 

/    XnHj 
Orthotoliiidin,  is  an  oily  liquid  at  a  temperature  at  which  paratoltiidin 


CH3 

/\ 

is  crystalline. 

\/ 

NH2 

The  prefixes  commonly  used,  ortho,  meta,  and  para,  refer  then  to  the  different 
forms  which  result  from  the  displacement  of  two  of  the  hydrogen  atoms  of 
the  ring.  When  there  are  more  than  two  substitutions  a  much  greater  num- 
ber of  isomeric  forms  is  possible,  and  these  are  designated  by  the  numbers  of 
the  angles,  1-2-3,  1-2-4,  1-3-5,  etc.    Dinitrophenol  1-2-4  is  this : 

HO 


/       NxOs 


NO2 

It  differs  toxicologically  from  all  the  other  isomers. 

"When  two  or  more  benzene  rings  are  joined,  as  in  naphthalene,  two  mono- 
substitution  products  are  formed,  according  as  the  substituting  atom  or  radical 
is  combined  with  a  carbon  atom,  which  is  in  direct  union  with  one  of  the 
common  carbon  atoms,  or  not.  These  two  forms,  known  as  alpha  and  beta, 
mav  be  Illustrated  as  follows : 


HO 


HO 


alpha-naphthol. 
NHa 


beta-naphthol. 


alpha-naphthylamine. 
SO3H 


NH, 


beta-naphthylamine, 


SO3H 


alpha-naphthalene-sulphoiuc  aeia 


beta-napnthalene-sulphoiiic  acid. 


APPENDIX  1. 


73 


The  compounds  thus  far  described  are  all  substitution  products  formed 
by  replacement  of  the  hydrogen  of  the  ring.  They  differ  in  chemical  and  physi- 
cal properties  and  in  their  effect  on  human  beings  from  the  substitution 
products,  which  are  formed  by  displacement  of  hydrogen  from  a  side  chain, 
such  as  the  radical  CH3.  Thus  if  the  hydrogen  of  the  ring  in  toluene  is  dis- 
placed by  NH2,  amidotoluene  or  toluidin,  is  formed,  while  if  the  replacement 
takes  place  in  the  CH3  radical,  we  have  benzylamine.  A  third  compound,  ^^^th 
the  same  elementary  composition,  results  when  the  replacement  is  in  the  NH2 
group  of  amidobenzene,  or  anilin.  and  a  CH3  radical  enters.  This  last  is  methyl 
anilin.     These  three  compounds  are  very  different  in  action  and  in  properties. 


Toluene. 
CH3 


Orthotoluidin. 

CH3 


NHj 


Benzylamine. 
CH2NH2 


Methyl  anilin. 
NHCH3 


\/ 


\/ 


This  distinction  is  very  important,  for  the  ring  substitutions  have  in  gen- 
eral the  physiological  action  of  benzene,  while  many  of  the  products  formed  by 
replacement  of  hydrogen  in  the  methyl  group  act  like  the  alcohols.  The  fol- 
lowing are  some  instances  of  these  two  kinds  of  products  :^ 


Ortliocresol. 
CH3 


HO 


Benzyl  alcohol. 
CH2HO 


/\ 


Chlortoluene,  formed  by  chlorine  gas  in  toluene  with  heat. 

CH3 

Cl 


Benzyl  chloride,  formed  by  chlorine  gas  in  toluene  with  cold. 

CH2CI 


Bodies  similar  to  benzene  substitution  products  may  be  formed  from  ammonia, 
H4N,  by  substitution  of  one  of  the  hydrogen  atoms.  Anilin  is  CcHsNHa.  Di- 
phenylamine  is  NH(CcH5)2. 

These  ammonia  substitution  products  are  slightly  toxic  if  at  all. 

An  instance  of  a  body  which  is  both  a  substitution  and  an  addition  product 
is  nitrosodimethylanilin 

N(CH3)2    ■ 


NO 

When  an  amido  compound  of  the  benzene  ring  is  acted  on  by  nitrous  acid, 
HNO2,  there  results  a  series  of  intermediate  compounds  known  as  diazo  com- 


^  Substitution  products  of  toluene  are  usually  called  tolyl  or  toluyl  compounds.  Toluyl- 
endiamine  is  C6H.3CH3(NH2)2.  Side-chain  products  are  called  benzyl.  Benzaldehyde  is 
CsHsCHO. 


74  INDUSTMAL,   POISOlSril^G  IlSr    MAKING    COAL-TAK   DYES. 

pounds  which  contain  two  nuclei  bound   together  by — N2 — .     Diazoamidoben- 
zene  is 

NHCsHs 

Anilin,  para  and  meta  pheuylendiamiue,  etc.,  yield  these  diazo  compounds,  and 
the  latter  unite  with  other  amido  compounds  or  with  phenols  to  form  azo  color- 
ing matters.  For  instance,  the  diazo  compound  of  benzidin  acting  on  alpha- 
naphthylamine  and  sulphuric  acid  forms  Congo  red. 

ALIPHATIC,  FATTY,  PARAFFIN  SERIES. 

These  bodies  are  hydrocarbons  derived  from  petroleum.  They  form  the 
methane  or  marsh  gas  series,  beginning  with  CH4  and  adding  successive  radicals 
of  CH2 ;  the  ethylene  series,  beginning  with  C2H4  and  adding  CH2 ;  and  the  acety- 
lene series,  beginning  with  C2H2.  Substitution  products  formed  wnth  HO  are 
alcohols ;  with  COOH,  acids ;  with  Cl,Br.I,  chlorides,  bromides,  iodides.  Alco- 
hols may  be  oxidized  to  aldehydes.  Amines  are  ammonia  substitution  products. 
To  illustrate : 

CH4,  marsh  gas  or  methane. 
CH2OH,  methyl  or  wood  alcohol. 
CHOH,  formaldehyde. 
CH3CI,  methyl  chloride. 
CHCI3,  chloroform. 
CH2COOH.  acetic  acid. 
C2H6,  ethane. 

C2H5HO,  ethyl  or  grain  alcohol. 
C2H4O,  acetaldehyde. 
C2H5XH2,  ethylamine. 
The  combinations  of  CH3,C2H5,  etc.,  with  the  benzene  ring,  have  already  been 
spoken  of. 

Methylanilin.  Dimethyl  anilin.  Diethvlanilin. 

CeHsNHCHs  CcH5N(CH3)2  CoH5X(C2H5)2 

APPENDIX  2.— PRODUCTS  DERIVED  FROM  COAL. 

The  diagram  facing  this  page  and  showing  the  products  derived  from  coal  and 
some  of  their  uses  is  reproduced  ))y  permission  of  the  Barrett  Co.,  of  New  York 
City,  by  whom  it  was  prepared. 

APPENDIX  3.— MASSACHUSETTS:  RULES  AND  REGULATIONS  SUG- 
GESTED FOR  SAFETY  IN  THE  MANUFACTURE  OF  BENZENE  DE- 
RIVATIVES AND  EXPLOSIVES.' 

Evidence  of  the  danger  to  the  life  and  to  the  health  of  persons  employed  in 
the  manufacture  and  use  of  various  benzene  derivatives  has  accumulated  in 
this  State  during  the  past  year.  The  experience  of  countries  where  manufac- 
turing processes  have  been  carried  on  in  an  extensive  way  for  many  years 
shows  that  the  industry  can  be  regulated  without  hindrance  to  its  development 
and  with  comparative  safety  to  the  workers  engaged  in  the  manufacturing 
processes. 

The  State  Board  of  Labor  and  Industries  presents  the  following  regulations 
to  insure  safety  to  the  workers  in  this  State,  and  will  welcome  any  observations 
manufacturers  or  employees  may  desire  to  make  on  these  proposals. 

CLASSIFICATION. 

The  following  substances  shall  come  within  these  regulations : 

Nitrobenzol.  Trinitrotoluene. 

Dinitrobenzol.  Anilin  hydrochloride. 

Dinitrotoluene.  Anilin  oil. 
Trinitrophenol  (picric  acid). 

Also  all  conTpounds  in  which  any  of  the  foregoing  is  a  part  of  the  manufac- 
turing process. 

2  Massachusetts.  State  Board  of  Labor  and  Industries.  Industrial  Bulletin  No.  11. 
Boston,   191fi. 


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254310—21.      (To  face  page  74.) 


APPENDIX   3.  75 

DANGERS. 

In  the  various  processes  of  manufacture  in  which  any  of  the  foregoing  sub- 
stances are  used,  a  danger  to  health  arises  in  three  ways,  viz : 

1.  From  the  inhalation  of  fumes  before  the  process  of  crystallization  is  com- 
pleted. 

2.  From  the  inhalation  of  dust  given  off  in  the  breaking  up  or  crushing  of  the 
crystallized  mass. 

3.  From  the  absorption  through  the  skin  by  contact  with  the  material  in 
either  the  liquid  or  solid  state. 

PREVENTION. 

The  danger  to  health  can  be  reduced  to  a  minimum  by — 

1.  The  removal  of  fumes  and  dust. 

2.  The  prevention  of  absorption  of  the  poisonous  material  through  the  skin. 
To  make  prevention  effective  the  fumes  and  dust  must  be  removed  at  or  very 

near  to  the  point  where  they  are  produced,  and  the  following  means  employed : 

A.   VENTILATION. 

1.  Every  vessel  containing  any  substance  included  in  these  regulations  shall, 
if  steam  is  passed  into  or  around  it,  or  if  the  temperature  of  the  contents  be 
at  or  near  the  temperature  of  boiling  water,  be  covered  in  such  a  way  that  no 
steam  or  vapor  may  be  discharged  into  the  open  air  at  a  less  height  than  25 
feet  above  the  heads  of  the  workers. 

2.  In  every  room  in  Avhich  fumes  from  any  of  the  substances  included  in  these 
regulations  are  evolved  in  the  process  of  manufacture  and  are  not  removed  as 
provided  in  section  1  there  shall  be  provided  and  maintained  thorough  ventila- 
tion by  means  of  a  fan  or  other  exhaust  system. 

3.  No  substances  mentioned  in  these  regulations  shall  be  crushed,  ground, 
mixed,  or  packed  in  a  crystalline  condition  except  with  an  efficient  exhaust  sys- 
tem, so  arranged  as  to  carry  away  the  dust  as  near  as  possible  at  its  point  of 
origin. 

4.  No  substances  mentioned  in  these  regulations  shall  be  broken  by  hand  in  a 
crystallizing  pan,  nor  shall  any  liquid  containing  it  be  agitated  by  hand,  except 
by  means  of  an  implement  at  least  6  feet  long  that  shall  prevent  the  workers' 
hands  and  faces  from  coming  into  close  proximity  with  the  substances  used. 

5.  In  the  filling  of  cartridges  with  any  of  the  substances  mentioned  in  these 
regulations,  the  process  shall  not  be  done  by  hand  except  by  means  of  suitable 
scoops. 

6.  Drying  stoves  shall  be  efficiently  ventilated  to  the  outside  air  in  such 
a  manner  that  hot  air  from  the  stoves  shall  not  be  drawn  into  the  workroom. 
No  person  shall  be  allowed  to  enter  a  stove  to  remove  the  contents  until  a  free 
current  of  air  has  been  passed  through  it.  All  openings  in  stoves,  retorts, 
vats,  etc.,  for  the  admission  of  workmen  into  the  interior  of  such  stoves,  vats, 
etc.,  shall  be  sufficiently  large  to  permit  the  easy  passage  of  the  body  of  such 
workmen. 

B.  WASHING  FACILITIES. 

There  shall  be  provided  and  maintained  in  a  cleanly  state,  in  good  repair, 
and  properly  lighted  for  the  use  of  all  persons  employed  on  the  substances 
mentioned  in  these  regulations — 

1.  At  least  one  washbowl,  sink,  or  other  appliance  for  every  five  persons, 
and  provided  with  running  hot  and  cold  water. 

The  number  of  bowls,  sinks,  or  other  appliances  required  shall  be  based 
upon  the  maximum  number  of  persons  entitled  to  use  the  same  at  any  one 
time.  Twenty  inches  of  sink  will  be  considered  as  equivalent  to  one 
washbowl. 

2.  A  lavatory  within  reasonable  access  and  under  cover,  with  a  sufficient 
supply  of  clean  towels  and  of  soap,  and  nail  brushes. 

3.  Sufficient  and  suitable  bath  accommodations  (shower  or  other)  with  hot 
and  cold  water,  and  a  sufficient  supply  of  soap  and  towels. 

C.  TOILET  FACILITIES. 

Rules  and  regulations  for  toilet  facilities  adopted  by  the  State  Board  of  Labor 
and  Industries  shall  prevail  in  all  establishments  where  the  manufacturing 
processes  concerned  in  these  special  regulations  are  carried  on. 


76  INDUSTRIAL  POISOlsriNG   II^T    MAKIlsTG   COAL-TAH  DYES. 

D.   SPECIAL  CLOTHING. 

There  shall  be  provided  and  maintained  for  the  use  of  all  persons  employed 
in  the  manufacturing  processes  incUided  in  these  regulations — 

1.  Suitable  overalls  or  suits  of  working  clothes.  Overalls  included  in  these 
regulations  shall  be  washed  or  renewed  at  least  once  every  vv^eek. 

2.  India-rubber  gloves,  which  shall  be  collected,  examined,  and  cleansed  at 
the  close  of  the  day's  work  and  shall  be  repaired  or  renewed  when  defective. 
Equivalent  protection  for  the  hands,  when  they  come  in  contact  with  the  sub- 
stances mentioned  in  these  regulations,  may  be  substituted  for  gloves. 

3.  Clogs  or  other  suitable  protection  for  footwear  that  shall  guarantee  against 
contact  with  the  siabstances  mentioned  in  these  regulations. 

4.  A  suitable  clothes  room  for  changing  and  for  keeping  clothing  put  off 
during  working  hours. 

5.  A  suitable  locker,  separate  from  the  clothes  room  and  meal  room,  for 
the  storage  of  overalls  and  other  work  clothes. 

E.  DINING  ROOM. 

1.  In  establishments  included  in  these  regulations  a  .suitable  meal  room 
shall  be  provided  unless  the  establishment  is  closed  during  the  meal  hours. 
This  dining  room  shall  be  separated  from  any  room  in  which  a  process  using 
materials  mentioned  in  these  regulations  is  carried  on. 

2.  Suitable  provisions  shall  be  made  for  the  keeping  of  food  brought  by 
persons  employed. 

3.  Adequate  washing  facilities,  equipped  with  running  hot  and  cold  water, 
shall  be  provided  in  or  adjacent  to  the  meal  room. 

4.  No  person  shall  introduce,  keep,  prepare,  or  partake  of  any  food,  drink, 
or  tobacco  in  any  room  in  which  a  process  using  substances  mentioned  in  these 
regulations  is  carried  on. 

MEDICAL  REQUIREMENTS. 

Each  establishment  in  which  manufacturing  proces.ses  using  materials  men- 
tioned in  these  regulations  are  carried  on  shall  employ  and  keep  in  employ- 
ment one  or  more  duly  qualified  physicians  to  act  as  medical  officer  or  officers, 
who  shall  be  in  attendance  at  all  necessai*y  times  while  .such  work  is  in  progress, 
so  as  to  guarantee  constant  medical  supervision  and  care  of  workers  engaged 
in  these  processes  of  manufacture. 

Such  medical  officer  shall  also  be  charged  with  the  duty  of  enforcing  the 
following  regulations : 

1.  Examine,  every  person  employed  in  these  processes  of  manufacture  either 
before  said  person  begins  employment,  or  within  seven  days  after  beginning  said 
employment. 

2.  Reexamine  every  person  employed  in  these  processes  at  least  once  in  each 
calendar  month,  or  at  such  other  intervals  as  may  be  necessary  to  insure  pro- 
tection to  the  workman  against  poisoning  from  the  substances  used  in  the 
process  of  manufacture ;  also  before  permitting  a  workman  to  return  to  work 
after  absence  or  suspension  on  account  of  Illness. 

5.  The  medical  officer  shall  have  the  power  of  suspen.sion  because  of  physical 
iTnfitness  of  any  person  employed  on  any  of  these  processes  of  manufacture, 
and  no  person,  after  such  suspension,  shall  be  reemployed  without  written 
sanction  of  the  medical  officer. 

4.  The  medical  officer  shall  give  such  instruction  to  employees  and  to  em- 
ployees concerning  the  danger  to  health  from  the  particular  process  of  manu- 
facture being  carried  on  in  the  establishment  as  will  best  qualify  such  persons 
to— 

(a)   Recognize  the  signs  of  poisoning. 

(6)  Apply  suitable  first-aid  treatment  to  workmen  taken  ill  upon  the 
premises. 

5.  The  medical  officer  shall  keep  a  full  and  complete  record  of  all  examina- 
tions made  by  him,  which  record  shall  contain  the  date  on  which  examinations 
are  made,  name,  address,  age,  height,  weight,  physical  condition  of  heart  and 
lungs  of  all  persons  examined  by  him ;  also  a  full  and  complete  record  of  all 
illnesses,  accidents  and  deaths  occurriug  among  the  employees  under  his  charge. 
These  records  .shall  be  open  to  the  inspection  of  the  State  board  of  labor  and 
industries  or  its  representatives,  and  a  copy  thereof  shall  be  forwarded  to  said 


APPENDIX  4.  77 

board  within  48  hours  following  the  occurrence  of  the  accident,  illness,  or  death, 
stating  as  fully  as  possible  the  cause  of  said  illness,  accident,  or  death  of 
employees. 

No  staiement  contained  in  any  such  report  shall  be  admissible  as  evidence 
in  any  action  arising  out  of  said  accident,  illness,  or  death  herein  reported. 

6.  There  shall  be  provided  a  suitable  medical  or  hospital  room  for  the  care 
and  treatment  of  workmen  taken  ill  upon  the  premises.  This  room  shall  be 
conveniently  located,  properly  lighted,  heated,  and  ventilated,  and  shall  con- 
tain the  following  minimum  equipment: 

(a)  A  couch  or  bed. 

(b)  Pair  of  blankets. 

(c)  Two  hot- water  bottles. 

(d)  Tank  of  oxygen,  with  apparatus  for  using  the  same, 

(e)  A  lungmotor. 

(f)  An  oxygen  helmet  for  rescue  work. 

(g)  Suitable  ropes  for  rescue  work. 

(h)  Medical  and  surgical  chest  as  prescribed  by  the  rules  of  the  State  board 
of  labor  and  industries. 

PRINTED  NOTICE  POSTED. 

A  printed  notice  in  language  intelligible  to  all  the  workers,  and  in  type 
sufficiently  large  to  be  legible  to  all  workers,  labeled  "  CAUTION,"  shall  be 
conspicuously  posted  and  maintained  in  all  departments  where  any  of  the  sub- 
stances mentioned  in  these  regulations  are  used  in  any  processes  carried  on 
therein.     Said  notice  shall  contain  the  following: 

1.  In  large  conspicuous  type  the  common  name  of  the  poisonous  substance  in 
use  in  that  particular  room. 

2.  That  the  substance  named  is  capable  of  causing  poisonous  symptoms  if 
precautions  are  not  observed, 

3.  Signs  and  symptoms  of  poisoning,  viz,  throbbing  of  blood  vessels,  giddi- 
ness, dizziness,  headache,  weakness  of  legs,  palpitation  of  heart,  nausea,  blue- 
ness,  cyanosis,  unconsciousness. 

4.  First-aid  treatment,  viz. : 

(a)   Remove  poisoned  person  to  the  fresh  air.     Keep  him  quiet  and  warm. 
(&)  Do  not  let  person  walk  home  until  advised  by  physician. 

(c)  Use  hot  coffee  as  stimulant, 

(d)  If  person  is  unconscious,  apply  artificial  respiration;  lungmotor;  oxygen 
inhalation ;  keep  patient  warm, 

5.  Prevention : 

(a)  Avoid  dust,  fumes,  and  chemical  compounds  on  hands,  feet,  and  clothes, 
( & )   Wash  hands  before  eating  and  after  day's  work  is  finished. 

(e)  Do  not  eat  food  nor  chew  tobacco  in  workroom. 

(d)  Do  not  wear  same  clothes  in  workroom  and  at  home. 

(e)  Use  extra  protection  on  hands,  feet,  and  clothes  while  at  work  on  any 
of  the  substances  mentioned  in  these  regulations. 

if)  Bathe  regularly. 

(g)  Consult  a  physician  if  losing  color  or  weight. 

(h)  Do  not  enter  stoves,  vats,  or  retorts  for  repair  work  unless  in  the  pres- 
ence of  another  workman. 

(i)   Have  emergency  appliances  ready  for  use  in  all  dangerous  repair  work. 

ij)  Watch  for  leaky  joints  in  pipes,  ducts,  valves,  etc.,  carrying  the  gas  or 
chemical  compounds. 

APPENDIX  4.— SAFETY  STANDARDS  FOR  THE  MANUFACTURE  OF 
NITRO  AND  AMIDO  COMPOUNDS  ADOPTED  BY  NEW  JERSEY 
AND  PENNSYLVANIA. 

Section  1.  For  the  purpose  of  these  regulations  the  following  nitro  and  amido 
compounds  shall  be  considered  injurious  to  health. 

(a)  The  nitro  compounds  of  benzol,  toluol,  xylol,  etc.,  as  well  as  their  chlo- 
rine derivatives. 

(b)  The  nitro  compounds  of  naphthaline. 

(e)   The  twice  or  higher  nitrated  compounds  of  phenol  and  naphthol. 

(d)  Aniline  and  its  homologues  (toluidine,  xylidine,  cumidine,  etc.),  anisi- 
dine,  phenetidine  and  their  chlorine,  nitro,  and  alphyl  derivatives,  as  dimethyl 
and  diethyl  aniline,  diphenylamine,  etc.  The  salts  of  these  compounds  are  com- 
paratively innocuous  and  do  not  come  under  these  regulations. 


78  UsTDUSTRIAL  POISOlSriNG   IN    MAKING    COAL-TAE   DYES. 

(e)   Phenylenediamine,  tolylenediamine. 

if)   Benzidine,  tolidine,  dianisdine. 

(g)  The  naphthylaniines.  The  salts  of  tliese  compounds  are  comparatively  in- 
nocuous and  do  not  come  under  these  regulations. 

(h)   Phenyl  and  tolyl  liydrazin. 

Factories  in  which  the  above  compounds  are  regularly  recovered  in  con- 
siderable quantities  are  mainly  : 

Fuchsin,  aniline  blue,  violet,  and  nigrosin  factories. 

Sec.  2.  Buildings. — The  buildings  in  which  nitro  and  amido  compounds  are 
manufactured  or  are  regularly  recovered  in  considerable  quantities  shall  be 
properly  ventilated. 

Buildings  in  which  twice  or  more  nitrated  compounds  of  benzol  or  of  toluene 
or  of  phenol  are  manufactured  shall  be  of  fire-resisting  material  or  shall  be 
separated  from  other  buildings. 

Sec.  3.  Platfoems. — In  the  above  buildings,  operating  platforms  may  be 
erected,  provided  they  do  not  cover  more  than  three-fourths  of  the  ground  floor. 
In  buildings  constructed  after  the  adoption  of  these  regulations,  the  distances 
of  platforms  (under  w^hich  workingmen  may  be  required  to  work)  from  the 
floor  and  from  each  other  shall  be  at  least  9  feet.  In  buildings  already  con- 
structed this  distance  shall  be  at  least  7  feet.  (It  is  recommended  to  leave  be- 
tween platforms  and  the  outer  walls  either  a  free  space  or  a  space  covered  by 
slats  18  inches  to  3  feet  wide ;  and  the  area  of  this  space  is  to  be  added  to  the 
free  space  in  calculating  the  latter.) 

On  top  of  melting  kettles  and  distilling  apparatus,  only  such  platforms  shall 
be  built  as  are  absolutely  necessary  for  the  proper  handling  of  the  apparatus, 
and  care  should  be  taken  that  all  apparatus  be  so  constructed  that  vapors  and 
gases  can  not  escape,  and  thereby  injure  those  obliged  (by  reason  of  their 
duties)  to  be  upon  said  platforms. 

Platforms  on  which  work  is  regularly  carried  on  with  nitro  and  amido  com- 
pounds shall  be  light  and  easy  to  clean  ;  covered  with  sheet  lead  where  advisable. 

Platforms  shall  be  equipped  with  railings  and  toe  boards,  in  accordance  with 
the  safety  standards  on  these  subjects  of  the  department  of  labor. 

Sec.  4.  Floors. — The  floor  of  the  workrooms  and  the  storage  room  shall  be 
nonabsorbent,  smooth,  and  easy  to  clean.  Where  necessary,  wooden  or  cement 
floors  are  permissible. 

Sec.  5.  Walls. — The  walls  of  the  workroom  shall  be  kept  clean.  If  painted 
with  calcimine  they  shall  be  repainted  at  least  once  a  year.  Windows  which 
can  be  opened  shall  be  provided  on  at  least  two  sides  of  the  room. 

Sec.  6.  Poor. — The  roof  shall  have  a  sufTicient  number  of  ventilators  or  other 
appliances,  which  allow  sufficient  ventilation  of  the  workroom,  and  which  can 
be  kept  open,  even  if  it  rains.  Windows  or  skylights  shall  be  so  constructed 
that  they  can  be  operated  from  the  floor  or  platform.  Skylights  in  the  roof 
shall  be  constructed  of  wire  glass. 

Sec.  7.  Manufactuee.- — The  work  in  the  above  factories  shall  be  regulated  in 
such  manner  that  the  men  do  not  come  in  direct  physical  contact  with  nitro  and 
amido  compounds.  It  is  therefore  recommended,  when  practicable,  that  liquid 
nitro  and  amido  compounds  be  transported  through  closed  pipe  lines  either  by 
pumping,  blowing,  suction,  or  by  gravity. 

As  a  general  rule  gravity  or  suction  is  to  be  preferred,  because  in  the  use  of 
compressed  air  fine  parts  of  the  compounds  go  olf  with  the  air.  It  is  also  neces- 
sary that  spent  compressed  air  be  vented  outside.  If,  in  the  latter  case,  this 
is  obnoxious  to  the  neighborhood,  it  is  suggested  that  the  spent  air  shall  be 
purified  before  being  expelled.  The  same  refers  to  the  air  which  is  expelled 
from  vacuum  pumps  of  distilling  apparatus,  as  it  frequently  contains  small 
quantities  of  anilin,  etc. 

Liquid  nitro  and  amido  compounds  shall  be  kept  and  stored  only  in  covered 
vessels.  Wherever  the  above  nitro  and  amido  compounds  are  handled  in  such 
a  manner  that  dust,  gases,  or  vapors  are  generated  (especially  in  powdering, 
sifting,  and  packing  operations),  the  work  shall  be  carried  on  as  far  as  practi- 
cable in  covered  or  closed  apparatus.  The  vapors  from  receivers  of  distillates 
shall  be  excluded  from  work  buildings. 

Chiseling  out  of  solid  nitro  and  amido  compounds,  which  are  explosive,  is 
strictly  forbidden ;  and,  when  these  are  poisonous,  is  permitted  only  if  proper 
precautions  are  taken. 

Drying  should  be  done  in  separate  buildings  used  for  drying  only,  or  in. 
properly  constructed  apparatus. 


APPENDIX  4.  79 

Frequently  drying  can  be  avoided  by  melting  the  nitro  and  amido  compounds, 
iind  breaking  them  up  when  cold. 

Where  boilers  are  fed  with  water  containing  aniline  the  boiler  shall  be  fitted 
with  suitable  safety  valves  and  water  glasses,  which  absolutely  prevent  the 
entering  of  steam  or  water  containing  aniline  into  the  workroom. 

Nitrating  apparatus. — In  nitrating  benzol  and  similar  compounds,  which  are 
readily  inflammable  or  generate  inflammable  or  explosive  vapors,  the  following 
precautions  must  be  observed : 

(a)  The  service  pipe  from  the  acid  container  to  the  nitrating  vessel,  where 
possible,  shall  be  of  such  a  diameter  that  at  no  time  can  an  excessive  amount 
of  acid  be  conducted  into  the  nitrating  tank.  The  diameter  of  this  pipe  must, 
of  course,  depend  entirely  on  the  size  of  the  container  which  it  supplies;  with 
acid. 

(&)  The  nitrating  tank  shall  be  fitted  with  a  safety  device  so  that  the  faucet 
of  the  acid  tank  can  not  be  opened  until  the  stirring  apparatus  of  the  nitrating 
tank  has  been  put  in  motion.  This  rule  is  due  to  the  fact  that  if  a  large 
quantity  of  acid  accumulates  in  the  bottom  of  the  nitrating  vessel  (due  to  its 
not  being  constantly  stirred)  a  powerful  chemical  reaction  will  occur  when  the 
stirrer  suddenly  starts  up,  and  there  is  sudden  combination  with  the  benzol. 

(c)  The  protruding  end  of  tlie  shaft  of  the  stirring  apparatus  shall  be  fitted 
with  a  pendulum  or  similar  device,  so  that  persons  in  charge  may,  from  a  dis- 
tance, know  that  the  stirring  apparatus  is  actually  in  motion  and  keeping  the 
mixture  constantly  agitated,  thus  preventing  undue  generation  of  heat. 

{d)  The  nitrating  vessel  must  be  equipped  with  a  large  pipe  (which  is  to  act 
in  the  capacity  of  a  safety  valve),  extending  through  the  roof,  and  provided  on 
top  with  a  suitable  arrangement,  which,  while  keeping  the  pipe  closed  ordi- 
narily, will  open  when  a  dangerous  pressure  developes  in  the  nitrating  vessel. 

When,  in  the  judgment  of  the  commissioner  of  labor  or  his  authorized  repre- 
sentative, it  is  deemed  necessary,  all  apparatus  and  machinery  in  which  nitro 
and  amido  compounds  are  manufactured,  transported,  treated,  distilled,  centri- 
fuged,  filtered,  dried,  ground,  mixed,  etc.,  packed  or  filled,  shall  be  fitted  with 
reliable  attachments  to  remove  such  dust,  gases,  or  vapors  as  may  be  generated. 

Special  care  shall  be  taken  so  that  all  vapors  generated  in  the  opening,  dis- 
charging, and  filling  of  dry  rooms,  melting  kettles,  autoclaves,  and  other  pres- 
sure vessels  will  be  harmlessly  disposed  of,  when  in  the  judgment  of  the  com- 
missioner of  labor  or  his  authorized  representative  it  is  deemed  necessary  to 
do  so. 

Sec.  8.  Cleanliness. — The  workroom  shall  be  kept  as  free  from  nitro  and 
fimido  compoxmds  as  possible.  If  any  of  the  above  compounds  are  spilled  they 
shall  be  removed  as  soon  as  possible.  The  floor  shall  be  cleaned  at  least  once 
every  24  hours. 

Sec.  9.  Health  precautions. — The  employer  shall  inform  the  workingmen 
employed  in  the  manufacture,  etc.,  of  the  above  nitro  and  amido  compounds 
as  to  the  poisonous  quality  of  these  products  and  the  necessity  of  strictly- 
observing  the  following  precautions : 

Shirts,  overalls,  caps,  stockings,  shoes,  gloves,  and  other  wearing  apparel 
which  have  become  saturated  with  poisonous  nitro  or  amido  compounds  in  such 
manner  that  the  skin  comes  in  immediate  contact  with  them  shall  be  imme- 
diately taken  off ;  the  skin  washed  first  with  vinegar  and  then  with  water ;  and 
the  employee  must  then  put  on  clothing  which  has  not  been  in  contact  Avith. 
these  substances. 

Employees  shall  be  warned  that  the  use  of  alcoholic  liquors  and  chewing 
tobacco  is  harmful  to  their  health.  Smoking  in  the  workroom  is  strictly  for- 
bidden. 

Food  shall  be  neither  kept  nor  eaten  in  the  workroom.  A  suitable  dining 
room,  absolutely  separate  from  the  workroom,  shall  be  provided.  Employees 
shall  not  be  allowed  to  enter  this  room  until  they  have  M^ashed  both  face  and 
hands.  For  this  purpose  wash  and  dressing  rooms  and  bathrooms,  absolutely 
separate  from  the  workroom,  shall  be  provided.  These  rooms  shall  be  suit- 
ably fitted  up,  kept  clean,  and  properly  heated.  Nobody  shall  be  alloAved  to 
keep  any  wearing  apparel  in  the  workroom.  All  process  men  shall  dress  in 
the  dressing  or  wash  room  provided.  Each  process  man  shall  be  provided  with 
two  lockers,  one  for  his  working  and  one  for  his  street  clothing,  or  a  properly 
divided  double  locker,  or  such  other  method  for  storing  clothing  as  shall  be 
approved  by  the  commissioner  of  labor  or  his  authorized  representative.  An 
approved  number  of  washing  appliances  shall  be  provided.  Soap  and  towels 
shall  be  furnished  in  suitable  number  and  free  of  charge. 


80  INDUSTRIAL  POISONING  IN    MAKING    COAL-TAE   DYES. 

It  is  recommended  that  every  working  man  who  comes  in  contact  with  the 
above  nitro  and  amido  compounds  shall  take  a  bath  daily  before  he  leaves  the 
factory. 

Men  who  suffer  from  inflammation  of  the  bladder  should  not  be  employed  in 
the  above  factories. 

Men  who  are  addicted  to  the  use  of  alcoholic  liquors  must  not  be  employed, 
and  no  employee  upon  whom  the  odor  of  alcoholic  liquor  is  detected  shall  be 
allowed  to  enter  the  factory. 

It  is  recommended  that  process  men  be  between  the  ages  of  22  and  50  years. 
It  is  also  recommended  that  applicants  for  employment  presenting  evidences 
of  anemia  or  of  emaciation  should  not  be  employed  as  process  men  by  reason 
of  their  increased  susceptibility. 

The  employment  of  females  except  in  the  office,  or  works  hospital,  or  welfare 
room  or  building,  is  prohibited. 

Toilets  shall  be  provided  in  accordance  with  the  sanitary  code  of  the  depart- 
ment of  labor. 

The  employer  shall  provide  and  maintain  a  sufficient  number  of  sanitary 
drinking  fountains,  readily  accessible,  for  the  use  of  all  employees. 

All  process  men  should  be  cautioned  of  the  danger  of  commencing  work  on  an 
empty  stomach. 

It  is  recommended  that  those  who  suffer  from  excessive  perspiration  should 
not  be  employed  as  process  men. 

Bodily  cleanliness  is  essential  to  good  health.  It  is  recommended  that  those 
employees  who  do  not  take  frequent  baths  be  not  employed  as  process  men. 

Process  men  are  those  employees  whose  work  brings  them  in  immediate  con- 
tact v.'ith  nitro  and  amido  compounds,  either  in  the  manufacture  of  these  com- 
pounds or  in  the  repair  of  apparatus  used  in  their  manufacture.  The  term 
does  not  include  employees  whose  duty  is  in  the  power  plants  or  other  em- 
ployees whose  work  does  not  bring  them  in  such  contact. 

Sec.  10.  Repairs. — All  repairs  and  changes  on  the  machinery,  apparatus,  and 
pipes  for  nitro  and  amido  compounds  shall  be  made  only  after  they  have  been 
thoroughly  cleaned. 

All  work  in  the  inside  of  apparatus,  vessels,  boilers,  etc.,  shall  be  done  in 
accordance  with  the  following  rules  of  procedure : 

If  it  is  necessary  for  an  employee  to  enter  vats,  tanks,  or  other  containers 
in  which  there  have  been  used,  stored,  or  manufactured  gases,  fumes,  or  vapors 
of  an  asphyxiating  or  poisonous  nature,  or  materials  which  give  off  gases, 
fumes,  or  vapors  of  an  asphyxiating  or  poisonous  nature,  the  following  pro- 
cedure shall  be  pursued  : 

(a)  Empty  containers.     Disconnect  and  blank  off  all  connections. 
(&)   Clean    containers    thoroughly   by   repeated    washings   with   water,    soda 
water,  steam,  compressed  air  or  other  suitable  means. 

(c)  If  the  person  in  charge  then  considers  conditions  satisfactory,  employees 
may  enter  such  containers.  They  miist  use  an  approved"  type  of  helmet,  and 
have  attached  to  their  bodies  a  life  line  or  rope  if  the  person  in  charge  con- 
siders it  necessary. 

(d)  The  life  line  or  rope  shall  be  under  the  control  of  one  or  more  fellow- 
workmen,  who  shall  remain  outside  of  the  container  in  order  that  they  may 
render  assistance  if  necessary. 

(e)  After  the  work  is  finished  the  men  should  take,  at  once,  a  bath  and 
change  their  clothing,  including  shoes,  if  the  foreman  or  other  person  in  charge 
shall  deem  it  necessary.     Facilities  for  taking  such  baths  shall  be  provided. 

The  superintendent  of  the  plant  shall  be  held  responsible  for  the  enforce- 
ment of  these  regulations. 

A  copy  of  the  rules  for  procedure  as  given  above  will  be  furnished  by  the 
department  of  labor  and  shall  be  conspicuously  posted  at  every  place  in  each 
plant  where  asphyxiating  or  poisonous  fumes,  gases  or  vapors  may  be  found. 

Sec.  11.  EESt^sciTATioN. — For  every  50  process  men  or  less  employed  in  such 
plant  and  exposed  to  such  risk  there  shall  be  present  at  all  times  at  least  2 
persons  who  are  trained  or  competent  to  apply  means  of  resuscitation  by  the 
prone  pressure  or  Shaeffer  method,  or  by  mechanical  devices  approved  by 
the  commissioner  of  labor. 

A  sufficient  number  of  helmets  of  a  type  approved  by  the  commissioner  of 
labor  shall  be  kept  at  each  plant,  in  order  that  they  may  be  available  for  use 
by  every  employee  who  has  occasion  to  enter  places  where  there  may  be  asphyx- 
iating or  poisonous  gases,  fumes  or  vapors. 


APPENDIX   4.  81 

All  employees  who  are  required  by  tlie  employer  to  wear  helmets  in  making 
repairs  or  in  maintenance  work  shall  be  thoroughly  instructed  iu  the  use  of 
such  apparatus;  and  be  physically  examined  by  a  licensed  physician  at  least 
once  in  ninety  days  or  after  absence  from  work  due  to  either  sickness  or 
accident.  The  physician  shall  certify  to  the  proper  physical  condition  of  the 
men  so  employed ;  and  no  employee  shall  be  permitted  to  do  such  repair  work 
unless  so  examined  and  certified.  The  examining  physician  shall  report  the 
results  of  these  examinations,  within  48  hours  after  each  examination,  to  the 
commissioner  of  labor,  upon  blanks  which  will  be  furnished  upon  request. 

Oxygen  inhalation  apparatus  shall  be  kept  on  hand  and  the  foremen  and 
authorized  employees  shall  be  instructed  in  its  use.  In  all  cases  in  which  the 
apparatus  lias  been  used,  a  physician  shall  at  once  be  called  or  the  sick  em- 
ployee removed  to  a  hospital.  A  supply  of  oxygen  or  the  means  for  its  produc- 
tion must  be  kept  on  hand. 

If  oxygen  tanks  are  used  at  least  two  must  be  kept  on  hand  at  all  times,  one 
of  which  shall  be  full. 

Sec.  12.  Physical  examination. — All  applicants  for  employment  as  process 
men  shall  be  physically  examined  by  a  licensed  physician,  either  before  com- 
mencing work,  or  before  the  expiration  of  24  hours  after  their  employment. 

All  process  men  shall  be  physically  reexamined  by  a  licensed  physician  at 
least  once  every  30  days,  and  before  resuming  work  after  an  absence  due  to 
sickness  or  to  accident  or  to  any  other  cause. 

These  examinations  shall  each  consist  in  the  determination  and  recording 
of  the  following  facts,  either  in  a  book  or  upon  a  card : 

Name    Age 

Address Process 

Height    Weight 

Examination  of  urine :  Reaction Specific  gravity 

Pulse Blood  pressure Hemoglobin 

Albumen Sugar Casts 


The  records  of  these  examinations  shall  at  all  times  be  open  for  inspection 
by  the  commissioner  of  labor  or  his  authorized  representative. 

The  examining  physician  shall  report  the  results  of  these  examinations  to 
the  commissioner  of  labor  within  48  hours  after  such  examinations,  upon 
blanks  which  will  be  furnished  upon  request. 

It  shall  be  the  duty  of  the  examining  physician  to  request  the  factory  man- 
ager or  superintendent  to  suspend  from  work  any  process  man  whom  he  be- 
lieves to  be  suffering  from  poisoning;  and  it  shall  be  his  further  diity  to  report 
such  case  to  the  department  of  labor  upon  the  following  blank : 

25431°— 21 6 


82 


INDUSTRIAL.  POISONING  IN   MAKING   COAL-TAR  DYES. 


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APPENDIX  4.  83 

When  in  the  judgment  of  the  conuiiissioiier  of  labor  it  is  necessary,  it  will 
be  the  duty  of  the  employer  to  provide,  without  expense  to  the  employee,  a 
hospital  room  or  dispensary,  separate  and  apart  from  the  workroom  or  rooms; 
which  room  shall  be  equipped  with  a  couch,  bed,  or  surgical  table,  two  pairs 
of  woolen  blankets,  two  hot-water  bottles,  two  tanks  (one  completely  full)  of 
oxygen,  and  the  necessary  apparatus  for  administering  the  same ;  an  oxygen 
heimet  for  rescue  work ;  such  device  or  devices  for  artificial  respiration  as  are 
appro^-ed  by  the  department  of  labor ;  and  a  shower  bath  with  hot  and  cold 
water ;  and  a  toilet,  which  toilet  shall  comply  with  the  sanitary  code  of  tlie 
department  of  labor. 

At  least  one  stretcher  shall  be  provided. 

It  sliall  be  the  further  duty  of  all  employers  to  keep  in  a  book  or  on  a  card 
a  record  of  all  employees,  showing  their  exact  employment  and  all  changes  to 
other  work ;  which  record  shall  at  all  times  be  open  for  inspection  by  the  com- 
missioner of  labor  or  his  authorized  representative. 

TRINITROTOLUOL. 

Section  13.  Scope. — Beyond  the  regular  regulations  for  the  erection  and  con- 
ducting of  factories  in  which  poisonous  nitro  and  amido  compounds  are  manu- 
factured, or  regularly  recovered  in  considerable  quantities,  the  following  addi- 
tional regulations  shall  govern  the  manufacture  of  trinitrotoluol  and  ammuni- 
tion derived  from  it. 

Sec.  14.  Buildings. — Trinitrotoluol  shall  be  manufactured  in  a  special  plant 
which  is  an  approved  distance  from  other  factories  or  portions  of  factories. 

Buildings  in  which  twice  or  more  nitrated  compounds  of  benzol,  or  twice  or 
more  nitrated  compounds  of  toluol  are  manufactured,  shall  be  of  fire  resisting 
material  or  shall  be  separated  from  other  buildings. 

Trinitrotoluol  factories  which  are  not  on  the  land  of  an  explosives  factory 
shall  be  surrounded  by  a  fence,  which  prevents  the  entrance  of  outsiders.  At 
the  gates  proper  signs  shall  be  provided,  which  prohibit  the  entrance  of  unau- 
thorized outsiders.     Smoking  upon  the  premises  shall  be  prohibited. 

Sec.  15.  Nitration. — Nitration  shall  be  performed  in  high  airy  rooms,  allow- 
ing easy  escape  of  vapors,  and  in  which  no  nitrated  product  is  stored  or  han- 
dled in  a  dry  condition.  There  shall  be  an  approved  number  of  easily  accessible 
exits. 

Sec  16.  Storage  of  acids. — Spent  acids  shall  be  stored  in  tanks,  standing  in 
the  open  air  and  only  roofed  over. 

Sec.  17.  Washing  and  centeifuging. — All  washing  and  centrifuging  opera- 
tions shall  be  performed  in  a  building  in  which  no  nitrated  product  is  stored. 
Ample  ventilation  shall  be  provided. 

Sec.  18.  Recrystallization. — The  recrystallizing  of  the  crude  trinitrotoluol 
with  easily  inflammable  solvents,  such  as  alcohol,  benzol,  or  toluol,  shall  take 
place  in  a  building  standing  alone.  AU  solution  tubs,  crystallizing  vessels, 
centrifuges,  and  conveying  apparatus,  shall  be  closed  in  such  manner  that 
vapors  in  dangerous  quantities  can  not  escape  into  the  workroom.  Proper  ven- 
tilation of  the  workroom  shall  be  provided.  All  platforms  in  this  building  shall 
have  an  exit  into  the  open  air. 

Sec  19.  Drying.— -The  drying  of  the  trinitrotoluol  shall  be  carried  on  in  a 
building  standing  alone.  The  separation  of  the  pure  trinitrotoluol  from  the 
solvent  may  be  done  in  the  building  for  the  recrystallizing,  if  the  apparatus 
provided  avoids  accumulation. 

Sec  20.  Packing.— All  packing  shall  be  done  in  separate  packing  houses. 

Sec.  21.  Storage.— Trinitrotoluol  shall  be  stored  in  separate  stock  rooms, 
protected  by  an  approved  type  of  barricade.  The  location  of  the  stock  rooms 
from  the  nearest  manufacturing  building  shall  be  at  an  approved  distance. 

Sec  22.  Storage  of  inflammable  solvents. — The  storage  of  tanks  of  inflam- 
mable solvents  or  of  toluol  shall  be  constructed  in  such  a  manner  that  the  con- 
tents of  the  tanks,  in  case  of  leakage,  can  not  run  over  the  surroundings.  Wher- 
ever practicable  storage  vessels  should  be  below  ground.  If  the  above  solvents 
are  stored  above  ground  they  shall  be  stored  in  an  approved  manner.  Storage 
in  open  air  in  iron  drums  in  a  suitable  place  is  permissible. 

Earth  embankments  of  sufficient  height  to  hold  the  contents  of  tanks  in  case 
of  leakage  shall  be  placed  around  all  tanks  of  inflammable  materials  when 
such  tanks  are  located  above  ground. 


.  84  i:n'dustiiial,  poisoin'ing  i]sr  makii^g  coal-tae  dyes. 

Sec.  23.  Manxttactltke  of  ammunition. — The  manufacture  of  ammunitiou 
from  trinitrotoluol  shall  be  conducted  in  a  separate  building  or  plant.  For 
the  storage  of  the  ammunition  the  same  regulations  govern  as  for  the  storage 
of  the  trinitrotoluol. 

Sec.  24.  Dooes. — ^All  doors  which  lead  into  the  open  air  shall  open  outward. 

Sec.  25.  Xiteating  appabatus. — All  nitrating  vessels  shall  have  reliable  ap- 
pliances for  stirring  and  for  the  regulation  of  the  temperature,  as  well  as 
ventilating  apparatus  for  the  removal  of  the  vapor. 

Sec.  26.  Dkying  apparatus. — If  the  drying  is  done  on  small  drying  hand 
trays  the  heating  elements  shall  be  arranged  in  such  a  manner  that  the  mate- 
rial to  be  dried,  or  the  dust,  can  not  come  in  direct  contact  with  them.  The  tem- 
perature in  the  drying  chambers  shall  not  exceed  60°  centigrade  [140°  Fahren- 
heit]. All  drying  apparatus  shall  be  constructed  in  such  manner  that  the  gases 
can  escape  easily  without  dangerous  pressure,  if  the  trinitrotoluol  should  ignite. 

If  the  drying  is  done  in  large  drying  pans,  hot  water  or  low-pressure  steam,  at 
not  over  20  pounds  pressure  i>er  square  inch,  shall  be  employed  for  heating. 
The  contents  shall  be  kept  in  constant  motion,  and  the  apparatus  shall  be  con- 
structed so  as  to  prevent  the  escape  of  vapors  into  the  workroom. 

Sec.  27.  Dust. — The  drying  and  sifting  apparatus  shall  be  so  constructed  as 
to  prevent  as  far  as  practical  the  escape  of  dust.  All  walls,  floors,  radiators, 
electric  bulbs,  etc.,  shall  be  kept  free  from  the  accumulation  of  trinitrotoluol 
dust.  All  employees  shall  be  provided  without  cost  with  respirators,  cloths, 
or  sponges,  for  their  protection  agamst  dust. 

Sec.  28.  Fiee  peeventiox. — In  rooms  in  which  there  are  easily  inflammable 
solvents  or  dried  TZS'T  (trinitrotoluol),  electric  motors,  electric  bells,  or  other 
sparking  apparatus  shall  not  be  employed.  Centrifugals  shall  neither  have  a 
brake,  nor  shall  it  be  allowed  to  brake  them  in  any  improvised  manner.  Oily 
waste  shall  be  kept  outside  the  workroom  in  safety  cans,  which  shall  be  cleaned 
frequently.  In  all  drying,  breaking,  and  sifting  operations  the  friction  of 
iron  against  iron  shall  not  be  permitted. 

Sec.  29.  Refuse. — Impure  trinitrotoluol  shall  be  relined  and  purified  before 
being .  used.  All  refuse  from  the  nitration  or  recrystallizing  rooms  which  is 
still  useful  shall  be  removed  from  the  above  rooms,  and  shall  be  kept  in  a 
special  room  until  it  is  refined.  It  shall  not  be  permissible  to  bury  any  refuse 
which  contains  trinitrotoluol.  Such  refuse  shall  be  placed  in  containers,  and 
shall  be  destroyed  from  time  to  time  under  the  supervision  of  an  experienced 
foreman. 

Sec.  30.  Repaies. — Repairs  on  apparatus  and  other  tools  which  have  been 
in  contact  with  trinitrotoluol  are  permissible  only  after  they  have  been 
thoroughly  cleaned.  The  remelting  of  old  vessels,  lead  pipe,  etc.,  is  permis- 
sible only  after  they  have  been  burned  off  on  an  open  fire.  AH  other  vessels, 
etc.,  which  have  become  useless,  shall  be  treated  in  the  same  manner  or  shall 
be  destroyed  by  explosion. 

Sec.  31.  Xitbic  acid. — In  view  of  the  danger  to  the  worker  from  inhalation 
of  nitrous  fumes  in  case  of  fire  or  of  the  breakage  of  carboys,  cai'boys  contain- 
ing nitric  acid  shall  be  stored  in  detached  sheds,  with  sandstone,  brick,  or 
other  suitable  flooring ;  and  in  quantities  not  to  exceed  100'  carboys  placed  in 
not  more  than  four  rows.  Xitric  acid  in  carboys  may  be  stored  in  the  open  in 
unlimited  quantities. 

The  following  notice  will  be  supplied  by  the  department  of  labor  on  applica- 
tion, and  shall  be  posted  at  all  places  in  plants  where  there  is  danger  of  poison- 
ing by  acid  fumes : 

ACID  FTJMES— WARNING. 
THE  INHALATION   OF  DENSE  ACID  FUMES  MAT   CAUSE  DEATH. 

Employees  are  strictly  prohibited  from  entering  buildings  where  dense  acid 
fumes  exist,  or  tanks  or  confined  spaces  which  are  not  entirely  clear  of  acid 
fumes,  unless  they  wear  a  helmet. 

Employees  working  in  such  places  shall,  in  addition  to  the  helmet,  wear  a  life 
line,  which  is  at  all  times  in  the  hands  of  an  assistant  stationed  outside  of  the 
tank. 

Employees  who  have  been  exposed  to  acid  fumes  and  who  feel  weak,  sick, 
short  of  breath,  or  who  are  attacked  with  cramps  or  coughing,  shall  report  this 
condition  to  their  foremen,  or  to  the  works  dispensary,  or  hospital,  at  once,  so 
that  proper  treatment  can  be  given.  They  must  not  wait  to  get  home.  Delay 
may  be  fatal. 


APPENDIX    5,  85 

Responsibility  for  complying  witli  these  regulations  shall  rest  with  the  fore- 
man or  other  person  designated  for  that  purpose  by  the  management  of  the 
plant. 

By  order  of — 

Commissioner  of  Laior. 

Water  shall  always  be  available  for  use  in  case  of  evolution  of  nitrous  funics 
caused  by  breakage  or  other  accident  to  carboys,  and  all  workers  handling  such 
acid  shall  be  warned  against  sprinkling  sand,  sawdust,  earth,  or  anything  other 
than  water  or  alkalies  upon  any  spilled  nitric  acid. 

At  all  places  where  there  is  danger  of  an  employee  becoming  burned  by  con- 
tact with  acid  there  shall  be  a  shower  bath. 

Sec.  32.  Avoidance  of  accumulations. — No  more  trinitrotoluol  shall  be  kept 
in  the  workroom  than  is  necessary  for  concurrent  use. 

CHEMICALS. 

Section  33.  Scope. — The  handling  and  storage  of  all  acids  and  other  chemicals 
necessary  for  the  operation  of  plants  not  herein  provided  for,  shall  be  governed 
by  regulations  as  set  forth  in  the  code  goveriing  the  operation  of  chemical 
works. 

Sec.  34.  Heating. — The  workrooms,  when  desirable,  shall  be  heated  by  an 
approved  system  of  steam,  indirect  hot  air  radiation,  or  hot  water.  The  tem- 
perature of  the  steam  shall  not  exceed  120°  Centigrade  [248°  Fahrenheit]. 
The  radiators  shall  be  at  least  1  inch  distant  from  all  wooden  walls  or  other  in- 
flammable material,  and  shall  be  attached  in  such  a  manner  that  they  can  be 
easily  inspected  and  cleaned. 

APPENDIX  5.— GREAT  BRITAIN:  REGULATIONS  FOR  THE  MANU- 
FACTURE OF  NITRO  AND  AMIDO  DERIVATIVES  OF  BENZENE 
AND  OF  EXPLOSIVES  WITH  USE  OF  DINITROBENZOL  OR  DINI- 
TROTOLUOL.' 

Whereas  the  manufacture  of  nitro  and  amido  derivatives  of  benzene,  and  the 
manufacture  of  explosives  with  use  of  dinitrobenzol  or  dinitrotoluol,  have  been 
certified  in  pursuance  of  section  79  of  the  factory  and  workship  act,  1901,  to  be 
dangerous ; 

I  hereby,  in  pursuance  of  the  powers  conferred  on  me  by  that  act,  make  the 
following  regulations,  and  direct  that  they  shall  apply  to  all  factories  and  work- 
shops in  which  the  said  manufactures  are  carried  on. 

Provided  that  regulations  1  (a),  2,  3,  4,  and  14  (c)  shall  not  apply  to  any 
process  in  the  manufacture  of  explosives  in  which  dinitrobenzol  is  not  used. 

DEFINITIONS. 

"  Employed  "  means  employed  in  any  process  mentioned  in  the  schedules. 

"  Surgeon  "  means  the  certifying  factory  surgeon  of  the  district  or  a  duly 
qualified  medical  practitioner  appointed  by  written  certificate  of  the  chief  in- 
spector of  factories,  which  appointment  shall  be  subject  to  such  conditions  as 
may  be  specified  in  that  certificate. 

"  Suspension  "  means  suspension  by  written  certificate  in  the  health  register, 
signed  by  the  surgeon,  from  employment  in  any  process  mentioned  in  the 
schedules. 

DUTIES. 

It  shall  be  the  duty  of  the  occupier  to  observe  Part  I  of  these  regulations. 
It  shall  be  the  duty  of  all  persons  employed  to  observe  Part  II  of  these 
regulations. 

PART  I.— DUTIES  OF  OCCUPIERS. 

1.  (a)  Every  vessel  containing  any  substance  named  in  schedules  A  or  B 
shall,  if  steam  is  passed  into  or  around  it,  or  if  the  tenrperature  of  the  contents 
be  at  or  above  the  temperature  of  boiling  water,  be  covered  in  such  a  way  that 
no  steam  or  vapor  shall  be  discharged  into  the  open  air  at  a  less  height  than  20 
feet  above  the  heads  of  the  workers. 

3  Great  Britain.      Home  Office.      Statutory  Rules  and  Orders,  1908.     No.  1310. 


86  INDUSTRIAL  POISONING  IN    MAKING   COAL-TAR   DYES, 

■  (&)  In  every  room  in  wliicli  fumes  from  any  substance  named  in  schedules  A 
or  B  are  evolved  in  the  process  of  manufacture  and  are  not  removed  as  above, 
adequate  through  ventilation  shall  be  maintained  by  a  fan  or  other  efficient 
means. 

2.  No  substance  named  in  schedule  A  shall  be  broken  by  hand  in  a  crystalliz- 
ing pan,  nor  shall  any  liquor  containing  it  be  agitated  by  hand,  except  by  means 
of  an  implement  at  least  6  feet  long. 

3.  No  substance  named  in  schedule  A  shall  be  crushed,  ground,  or  mixed  in  the 
crystalline  condition,  and  no  cartridge  filling  shall  be  done,  except  vpith  an 
efficient  exhaust  draught  so  arranged  as  to  carry  avpay  the  dust  as  near  as 
possible  to  the  point  of  origin. 

4.  Cartridges  shall  not  be  filled  by  hand  except  by  means  of  a  suitable  scoop. 

5.  Every  drying  stove  shall  be  efficiently  ventilated  to  the  outside  air  in  such 
manner  that  hot  air  from  the  stove  shall  not  be  drawn  into  any  workroom. 

No  person  shall  be  allowed  to  enter  a  stove  to  remove  the  contents  until  a  free 
current  of  air  has  been  passed  through  it. 

6.  A  health  register,  containing  the  names  of  all  persons  employed,  shall  be 
kept  in  a  form  approved  by  the  chief  inspector  of  factories. 

7.  No  person  shall  be  newly  em-ployed  for  more  than  a  fortnight  without  a  cer- 
tificate of  fitness  granted  after  examination  by  the  surgeon  by  signed  entry  in 
the  health  register. 

8.  Every  person  employed  shall  be  examined  by  the  surgeon  once  in  each 
calendar  month  (or  at  such  other  intervals  as  may  be  prescribed  in  writing  by 
the  chief  inspector  of  factories)  on  a  date  of  which  due  notice  shall  be  given  to 
all  concerned. 

9.,  The  surgeon  shall  have  power  of  suspension  as  regards  all  persons  em- 
ployed, and  no  person  after  suspension  shall  be  employed  without  written  sanc- 
tion from  the  surgeon  entered  in  the  health  register. 

10.  There  shall  be  provided  and  maintained  for  the  use  of  all  persons  em- 
ployed— 

(a)  Suitable  overalls  or  suits  of  working  clothes  which  shall  be  collected  at 
the  end  of  every  day's  work,  and  (in  the  case  of  overalls)  washed  or  renewed 
at  least  once  every  week ;  and 

(6)  A  suitable  meal  room,  separate  from  any  room  in  which  a  process  men- 
tioned in  the  schedules  is  carried  on,  unless  the  works  are  closed  during  meal 
hours;  and 

(c)  A  suitable  cloakroom  for  clothing  put  off  during  working  hours ;  and 

(d)  A  suitable  place,  separate  from  the  cloakroom  and  meal  room,  for  the 
storage  of  the  overalls. 

For  the  use  of  all  persons  handling  substances  named  in  the  schedules — 

(e)  India-rubber  gloves,  which  shall  be  collected,  examined,  and  cleansed,  at 
the  close  of  the  day's  work,  and  shall  be  repaired  or  renewed  when  defective, 
or  other  equivalent  protection  for  the  hands  against  contact. 

For  the  use  of  all  persons  employed  in  processes  mentioned  in  schedule  A — 
if)  Clogs  or  other  suitable  protective  footwear. 

11.  There  shall  be  provided  and  maintained  in  a  cleanly  state  and  in  good 
repair  for  the  use  of  all  persons  employed — 

A  lavatory  under  cover,  with  a  sufficient  supply  of  clean  towels,  renewed 
daily,  and  of  soap  and  nail  brushes,  and  with  either — 

(a)  A  trough  with  a  smooth  impervious  surface,  fitted  with  a  waste  pipe 
without  plug,  and  of  such  length  as  to  allow  at  least  2  feet  for  every  five  such 
persons,  and  having  a  constant  supply  of  warm  water  from  taps  or  jets  above 
the  trough  at  intervals  of  not  more  than  2  feet ;  or 

(7j)  At  least  one  lavatory  basin  for  every  five  such  persons,  fitted  with  a 
waste  pii^e  and  plug  or  placed  in  a  trough  having  a  waste  pipe,  and  having  either 
a  constant  supply  of  hot  and  cold  water  or  warm  water  laid  on,  or  (if  a  con- 
stant supply  of  heated  water  be  not  reasonably  practicable)  a  constant  supply 
of  cold  water  laid  on  and  a  supply  of  hot  water  always  at  hand  when  required 
for  use  by  persons  employed. 

For  the  use  of  all  persons  employed  in  processes  mentioned  in  schedules  A 
and  B— 

(c)  Sufficient  and  suitable  bath  accommodation  (douche  oi-  other)  with  hot 
and  cold  water  laid  on  and  a  sufficient  supply  of  soap  and  towels.  Provided 
that  the  chief  inspector  may  in  any  particular  case  approve  of  the  use  of  public 
baths,  if  conveniently  near,  under  the  conditions  (if  any)  named  in  such 
approval. 


APPENDIX   5.  87 

12.  No  person  sliall  be  allowed  to  introduce,  keep,  prepare,  or  partake  of 
any  food,  drink,  or  tobacco  in  any  room  in  which  a  process  mentioned  in  the 
schedules  is  carried  on. 

PART  II.— DUTIES   OF  PERSONS   EMPLOYED. 

13.  Every  person  employed  shall — 

(a)  Present  himself  at  the  appointed  time  for  examination  by  the  surgeon  as 
provided  in  regulation  8  ; 

(&)  Wear  the  overalls  or  suit  of  working  clothes  provided  under  regulation 
10  (a)  and  deiwsit  them,  and  clothing  put  off  during  working  hours,  in  the 
places  provided  under  regulation  10  (c)  and  (d)  ; 

(c)  Use  the  protective  appliances  supplied  in  respect  of  any  process  in  which 
he  is  engaged; 

id)  Carefully  clean  the  hands  before  partaking  of  any  food  or  leaving  the 
premises ; 

(e)  Take  a  bath  at  least  once  a  week,  and  when  the  materials  mentioned  in 
the  schedules  have  been  spilt  on  the  clothing  so  as  to  wet  the  skin.  Provided 
that  (e)  shall  not  apply  to  persons  employed  in  processes  mentioned  in  schedule 
C,  nor  to  persons  exempted  by  signed  entry  of  the  surgeon  in  the  health  register. 

14.  No  person  employed  shall — 

(a)  After  suspension,  work  in  any  process  mentioned  in  the  schedules  with- 
out written  sanction  from  the  surgeon  entered  in  the  health  register ; 

(6)  Introduce,  keep,  prepare,  or  partake  of  any  food,  drink,  or  tobacco  in  any 
room  in  which  a  process  mentioned  in  the  schedules  is  carried  on ; 

(c)  Break  by  hand  in  a  crystallizing  pan  any  substance  named  in  schedule 
A  or  agitate  any  liquor  containing  it  by  hand,  except  by  means  of  an  imple- 
ment at  least  6  feet  long ; 

(d)  Interfere  in  any  way,  without  the  concurrence  of  the  occupier  or  man- 
ager, with  the  means  and  appliances  provided  for  the  removal  of  the  fumes 
and  dust,  and  for  the  carrying  out  of  these  regulations. 

SCHEDULES. 

A.  Processes  in  the  manufacture  of — 

Dinitrobenzol. 
Dinitrotoluol. 
Trinitrotoluol. 
Paranitrochlorbenzol. 

B.  Processes-  in  the  manufacture  of — 

Anilin  oil. 

Anilin  hydrochloride. 

C.  Any  process  in  the  manufacture  of  explosives  with  use  of  dinitrobenzol  or 
dinitrotoluol. 


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OF  THIS  PUBLICATION  MAY  BE  PROCURED  FROM 

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V 


(Continued  from  second  page  of  cover.) 

•1910-1912,  Report  on  condition  of  woman  and  child  wage  earnere  In  the  United 
States  (S.  Doc.  645,  Gist  Cong.,  2d  sess.)  : 
Vol.  I,  Cotton  textile  industry. 
Vol.  II,  Men's  ready-made  clothing. 
Vol.  Ill,  Glass  industry. 
Vol.  IV,  Silk  Industry. 

Vol.  XI,  Employment  of  women  In  the  metal  trades. 
Vol.  XII,  Employment  of  women  in  laundries. 

Vol.  XIV,  Causes  of  death  among  woman  and  child  cotton-mlU  operatives. 
Vol.  XVII,  Hookworm  disease  among  cotton-mill  operatives. 
Vol.  XVIII,  Employment  of  women  and  children  In  selected  industrle.s. 
Vol.  XIX,  Labor  laws  and  factory  conditions. 
Bui.  98,  January,  19l2,  Conciliation,  arbitration,  and  sanitation  in  the  cloak,  suit, 

and  skirt  Industry  in  New  York  City. 
Bui.  100,  May,  1912,  List  of  industrial  poisons  and  other  substances  injurious  to 
health  found  iu  industrial  processes. 

A  liat  of  bulletins  iatued  aince  July  1,  1912,  In   the  series   "Industrial  Accidents  and 
Hygiene  "  is  as  follows: 

Bui.  104,  August,    1912,    Lead    poisoning    in    potteries,    tile    works,    and    porcelain 

enameled   sanitary   ware,  factories. 
Bui.  120,  May,  1913,  Hygiene  of  the  painters'  trade. 
Bui.  127,  August,  1913,  Dangers  to  workers  from  dusts  and  fumes,  and  methods  of 

protection.  ' 

Bui.  141,  February,  1914,  Lead  poisoning  in  the  smelting  and  refining  of  lead. 
Bui.  157,  March,  1915,  Industrial  accident  statistics. 

Bui.  165,  December,  1914,  Lead  poisoning  in  the  manufacture  of  storage  batteries. 
Bui.  179,  October,  1915,  Industrial  poisons  used  in  the  rubber  industry. 
Bui.  188,  March,  1916,  Report  of  British  department  committee  on  the  danger  in 

the  use  of  lead  in  the  painting  of  buildings. 
Bui.  201,  August,  1916,  Report  of  the  committee  on  statistics  and  insurance  cost  of 

the   International   Association   of    Industrial    Accident   Boards   and    Commissions. 

[Limited  edition.] 
Bui.  205,  January,  1917,  Anthrax  as  an  occupational  disease. 
Bui.  207,  March,  1917,  Causes  of  death  by  occupation. 
Bui.  209,  April,  1917,  Hygiene  of  the  printing  trades. 

Bui.  216,  Augus.t,  1917,  Accidents  and  accident  prevention  in  machine  building. 
Bui.  219,  May,   1917,   Industrial   poisons  used  or  produced   in   the   manufacture   of 

explosives. 
Bui.  221,  April,  1917,  Hours,  fatigue,  and  health  in  British  munitions  factories. 
Bui.  230,  July,  1917,  Industrial  efficiency  and  fatigue  in  British  munitions  factories. 
Bui.  231,  June,  1918,  Mortality  from  respiratory  diseases  in  dusty  trades. 
Bui.  234,  June,  1918,  Safety  movement  in  the  iron  and  steel  industry,  1907  to  1917, 
Bui.  236,  July,  1918,  Effect  of  the  air  hammer  on  the  hands  of  stonecutters. 
Bui.  251,  October,  1919,  Preventable  deaths  in  the  cotton  manufacturing  industry. 
Bui.  253,  February,  1919,  Women  in  the  lead  industry. 
Bui.  256,  November,  1919,  Accidents  and  accident  prevention,  in  machine  building. 

Revision  of  Bui.  216. 
Bui.  267,  July,  1920,  Anthrax  as  an  occupational  disease.      (Revised.) 
Bui.  276,     September,  1920,  Standardization  of  industrial  accident  statistics. 
The  following  bulletins,  published  since  July  J,  1912,   but  not   included   in    the   seriea 
"Industrial  Accidents  and  Hygiene,"    also  contain  irnportant   material  relating   to   the 
subject  of  industrial  hygiene  : 

Bui.  101,  July,  1912,  Care  of  tuberculous  wage  earners  In  Germany. 

Bui.  122,  May,  1913,  Employment  of  women  In  power  laundries  in  Milwaukee. 

Bui.  142,  February,   1914,  Administration  of  labor  laws  and  factory  inspection  in 

certain  European  countries. 
Bui.  145,  April,  1914,  Conciliation,  arbitration,  and  sanitation  in  the  dress  and  waist 

industry  of  New  York  City. 


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